摘要:

J. CHEM. SOC. DALTON TRANS. 1990 Structural Trends in Phosphine-substituted [RUCO~R~,-,H(CO),~] ( x = 0-3) Clusters. Crystal Structures of [RuCo,H(CO),,(PR,)] (PR = PMe or PMe,Ph) [RuCo2RhH(CO),,(PMe,Ph)] [RuCo,Rh,-,H(CO),,(PPh,),l [RuRh,H(CO),,(PR,)] (PR = PMe or PMe,Ph)t Jussi Valkonen Department of Chemistry University of Jyvaskyla SF-401 00 Jyvaskyla Finland Jouni Pursiainen," Markku Ahlgren and Tapani A. Pakkanen * Department of Chemistry University of Joensuu P. 0. Box 11 I SF-80101 Joensuu Finland The crystal structures of [ RuCo,H (CO), ( PMe,)] [ RuCo,H (CO),,( PMe2Ph)] [RuCo,RhH (CO),,- ( p M e2Ph) 1 I [ Ru Coi .75Rhi .25H (co) l o ( pph3)21 [ Ru CoRh2H (co) 10 ( pph3)2l CRURh3H (co) 11 ( PMe3) 1 I and [RuRh,H(CO),,(PMe,Ph)] ligand arrangements with phosphines on show [Rh,(CO),,]-like basal rhodium or cobalt atoms.The phosphines are axially co-ordinated except in the last two compounds where equatorial co-ordination is found. Hydrides bridge Ru-R h edges in [RuR~,H(CO),,(PR,)] (PR = PMe or PMe,Ph) and basal M faces in the other compounds. Geometric parameters are discussed with respect t o the metal combination or ligand site. Systematic synthesis and characterization of mixed-metal clusters is important for the development of a theoretical understanding of the influence of the metal composition on the properties of such compounds. Trends in structural and physical properties and chemical reactivity for a large group of clusters are valuable for the understanding of the role of a particular element in a mixed-metal cluster.Tetranuclear dodecacarbonyl mixed-metal clusters of cobalt rhodium and ruthenium [M,H,(CO),,] (x = 0-4) form an exceptionally large and well defined group of isoelectronic compounds. The parent carbonyl clusters of this group have been synthesized and characterized except for [CoRh3- (CO)12] which is un~table.~ These compounds can be expected to be important in studies of the influence of different metal combinations on the cluster properties especially because most of the compounds have similar [Rh,(CO) ,]-like carbonyl arrangements. Phosphine-substituted derivatives of [Co,Rh - ,(CO) 2] (x = 0 or 2 - 4 ) have been widely studied.8 We have previously studied trends in the hydride positions reactivity with phosphines and 'H chemical shifts of [RuCo,Rh -,H(CO) ,] (x = 0-3) and [ R U ~ C O R ~ - ~ H ~ ( C O ) ~ ~ ] (x = 0-2) clusters and their phosphine derivative^.'*'^ In this work representative crystal structures of phosphine- substituted derivatives of [RuCo,Rh -,H(CO),,] (x = &3) have been determined and the structural differences observed with different metal compositions are discussed.The com- pounds are [RuCo,H(CO) '(PMe,)] (l) [RuCo,H(CO) 1- (PMe2Ph)l (21 [RuCo2RhH(CO)l 1(PMe2Ph)1 (31 CRuCo1.75- Rh,.25H(CO)lo(PPh3)21 (4) CRuCoRh,H(CO)lO(PPh,)21 (5) [RuRh,H(CO) ,(PMe,)] (6) and [RuRh,H(CO) ,(PMe,Ph)] Rh-P (7). Results and Discussion We have previously observed in solution systematic trends in hydride positions reactivity with phosphines and 'H n.m.r.chemical shifts of [RuCo,Rh,~,H(CO),,] ( x = 0-3) and [Ru,Co,Rh2~,H,(C0),,] ( x = 0-2) clusters and their phos- phine derivatives." The crystal structures in this study were determined to establish in the solid state the main structural features deduced from the 'H n.m.r. data and to obtain data on (6) 1147 ( x = 1-2). and h-P ( 7 ) Figure 1. Schematic structures of the seven compounds (1)-(7) showing the sites of metal atoms hydride (H) and phosphine (P) ligands possible geometric trends with respect to the metal combin- ations or ligand sites. Schematic diagrams of the compounds are presented in Figure 1 and the crystal structures and numbering schemes of (2) (5) and (7) in Figures 2 3 and 4 respectively. Metal-metal distances are presented in Table 1 metal-carbon metal-phosphorus and carbon-oxygen bond lengths in Table 2 and structurally important bond angles in Table 3.All the compounds studied have closed tetrahedral metal cores surrounded by nine terminal carbonyl/phosphine ligands three carbonyls bridging the basal metals and one hydride ligand. In (5) however carbony18 semibridges the Ru(l)-Co(l) bond [Ru(l)-C(8) 253.1(6) and Co(l)-C(8) 176.2(9) pm]. t Supplementary data available see Instructions for Authors J. Chem. SOC. Dalton Trans. 1990 Issue 1 pp xix-xxii. 1148 Table 1. Metal-metal bond lengths (pm) in [RuCo,H(CO) 1(PMe3)] (l) [RuCo,H(CO) l(PMe,Ph)] (2) [RuCo,RhH(CO) l(PMe,Ph)] (3) CRuCo .~~R~,.~~H(CO)~O(PP~~)ZI (41 [ R ~ C ~ R ~ H ( C O ) ~ ~ ( P P ~ ~ ) Z I (5) [RuRh3H(C0)1 I(PM~J)I (6) and [RuRh3H(CO)1 1(PMe2Ph)l (7) (3) (2) 256.4(1) 256.6( 1) 256.q 1) 270.7(1) 264.2( 1) 265.3( 1) (1) 265.9(4) 266.9(4) 266.7(4) 252.5(5) 252.8(4) 251.5(5) 261.5(1) 261.9(1) 256.5(1) 250.4(2) 249.1(1) 248.6(1) Ru( 1)-M( 1) Ru( 1)-M(2) Ru( 1)-M(3) M(l)-M(2) M(lFM(3) M(2)-M(3) The Ru-Rh and Rh-Rh bonds are in bold and the Co-Rh bonds in italic type.Figure 2. Crystal structure and numbering scheme of [RuCo,H(CO) (PMe,Ph)I (2) 3. Crystal structure and numbering scheme of [RuRh3H(CO) 1- Ph)l (7) The apical metal is ruthenium in all the compounds and phosphines are co-ordinated to basal cobalt or rhodium atoms. Due to the higher reactivity of rhodium with respect to cobalt cobalt sites are occupied by phosphines only in compounds where no free rhodium sites are a~ailable.~ Phosphines are axially co-ordinated in (1 j ( 5 ) and equatorially co-ordinated in (6) and (7).Equatorial phosphines are not common in mono- or di-substituted derivatives of [M4Hx(p-C0)3(C0)9] clusters (M4 is a combination of Fe Ru Co or Rh),' although examples J. CHEM. SOC. DALTON TRANS. 1990 (7) (4) (5) 274.9(1) 275.2(1) 266.4(2) 277.0(1) (6) 286.8(2) 272.4(3) 272.8(2) 272.2(2) 273.8(2) 279.2(2) 266.1(1) 267.9(1) 269.9(2) 266.7(3) 266.3(3) 264.8(3) 259.5(3) 257.5(3) 287.0(1) 274.4(1) 2725(1) 273.8(1) 272.9(1) 281.9(1) Figure 4. Crystal structure and numbering scheme of [RuCoRh,H- (CO),O(PPh,),l (5) like [Rh4(CO)10(PPh3)2 J are known.In the corresponding tri- and tetra-substituted clusters some of the phosphines are equatorially co-ordinated due to steric restrictions. The hydride sites can be inferred from the data in Tables 1 and 3. The Ru(1)-Rh(1) bonds in compounds (6) and (7) are significantly longer than the other Ru-Rh distances as a result of the hydride bridge. The carbonyls also bend away from these bridged Ru-Rh edges as a result of the steric demands of the hydrides. The angles Ru(1)-Rh(1)-P(1) (1 17.4 and 115.3') Rh(1)-Ru( l)-C(l) (107.7 and 106.8') and Rh(1)-Ru(1)-C(3) (105.5 and 108.2') are significantly larger than other correspond- ing angles. The large Rh(3)-Ru(l)-C(l) and Rh(3)-Ru(l)-C(2) angles in compound (5) are caused by the repulsion of the semibridging carbonyl CO(8).The average M-M-C,,/P, (M = Co or Rh) values are 119.6 116.8 118.7 118.9 123.3 105.2 and 107.3O for compounds (l) (2) (3) (4) (5) (6) and (7) showing the angle opening due to M,(p-H) hydride in (1)-(5)- In solution equatorial phosphines are connected with edge- bridging Ru(p-H)Rh hydrides and axial phosphines are con- nected with face-bridging M,(p-H) (M = Co or Rh) hydrides so that for the rhodium-containing compounds both isomers are present in different relative abundances. The relative abundance of the equatorial co-ordination of phosphines together with the Ru(p-H)Rh hydrides increases with the metal combination (independent of the type of phosphine ligand) in the order RuCo2Rh < RuCoRh < RuRh, whereas for [RUCO,H(CO)~ 2] derivatives only axial phosphines are f ~ u n d .~ . ' ~ Additionally the relative abundancies of the Ru(p-H)Rh forms increase with different ligands in the order PPh < PMePh < PMe,Ph < PMe,.'' The forms that are dominant in solution were those found in the crystal state [Ru(p-H)Rh for (6) and (7) and M,(p-H) for the other J. CHEM. SOC. DALTON TRANS. 1990 Table 2. Metal-carbon metal-phosphorus and carbon-oxygen bond lengths (pm) in compounds (1)-(7) Table 3. Selected bond angles (") for compounds (1)-(7) (2) 187.9( 1 1) 189.6( 11) 187.9(9) 222.8(2) 176.4(9) 176.6(9) 180.1(8) 177.7(8) 183.8(8) 189.2(9) 190.6( 8) 198.9(9) 196.0(9) 2OO.5( 10) 195.8( 11) 113.3(13) 109.0( 14) 110.3(11) 112.5(12) 1134 12) 1 1 1.1 (10) 1 12.4( 10) 110.3(11) 120.7( 10) 117.8( 13) 1 15.4( 15) (1) 96.8(8) 100.5(8) 107.3( 10) 103.7(9) 99.7( 1 1) 102.0( 12) 83.5(9) 74.7( 1 1) 76.1( 10) 179.3(3) 11733) 117.7(3) 176.3(9) 118.5(9) 121.7(9) 176.5(11) 12 1 4 10) 120.8( 10) 146.0(24) 142.5(21) 134.2(22) 144.4(24) 134.5(20) 137.3(24) (3) 190.3( 1) 192.6(5) 19 1.0(5) 233.4(1) 188.3(5) 176.6(5) 179.4(4) 178.0(4) 1 82.1 (4) 208.2(4) 209.6(4) 20 1.9( 5 ) 198.9(5) 199.0(5) 196.8(6) 113.4(6) 1 12.1(7) 113.2(6) 112.5(7) 114.6(6) 112.8(5) 113.0(5) 11 1.8(5) 115.0(5) 115.3(6) 115.6(8) (3) 94.6( 1) 97.5(1) 106.8( 1) (2) 9733) 97.8(2) 100.5(3) 100.8(3) 9733) 99.8(3) 88.5(3) 83.6(3) 84.9(2) 175.8( 1) 11 7.1( 1) 1 14.9( 1) 177.6(3) 117.3(3) 1 17.0(3) 177.6(3) 116.8(3) 117.5(3) 143.8(9) 142.9( 8) 135.8(8) 139.9(8) 138.0(7) 141.1(8) 105.0( 1) 95.2(1) 101.3(1) 90.8(2) 72.8(2) 78.4(1) 172.2(1) 116.5(1) 1 12.6( 1) 174.5(2) 123.4(2) 121.5(1) 179.4(2) 118.8(2) 119.1(2) 140.8(4) 138.3(4) 140.0(4) 138.9(4) 141.9(4) 1 40.2( 4) (5) 190.5(9) 19 1.1(8) 189.2(6) 237.9(2) 23 7.1 (2) 188.0( 7 ) 186.6(7) 175.8(8) 1 76.6( 7 ) 21 2.2(6) 21 0.0(6) (4) 181(2) 188(3) 183(2) 232.1 (5) 229.1(6) 176(2) 178(2) 171(2) 172(2) 201 (2) 197(2) 196(2) 199(2) 196(2) 194(2) 1 18(3) 115(2) 1 18(2) 118(2) 11 5(2) 1 18(3) 118(2) 120(2) 120(2) 119(2) 21 1.6(5) 210.8(5) 199.6(7) 200.6(7) 113.6( 12) 113.8(1) 114.5(8) 112.4(8) 113.7(9) 1 16.2(9) 1 1 5.1(9) 115.8(6) 116.3(9) 115.5(8) (4) 99.7(2) 100.9(1) 1OO.3( 1) 101.7( 1) 98.4(2) 101.5(2) 88.7(2) 7 8.0(2) 76.0( 1) 172.6(1) 113.0( 1) 114.5(1) 177.0(1) 119.7(2) 122.1( 1) 175.7(2) 120.7(2) 123.1(2) 138.2( 15) 14 1.5( 14) 137.5(15) 140.3( 14) 1 3 5.2( 12) 137.8( 13) (5) 96.7(3) 1 O4.9(2) 102.9(3) 108.0( 2) 94.4(2) 94.3(3) 83.2(2) 84.9(2) 66.2(2) 175.4( 1) 123.8( 1) 119.6(1) 174.9(1) 124.3( 1) 1 19.7( 1) 1 6 9 3 3) 125.5(2) 126.8(3) 138.4(5) 138.2(5) 139.3(5) 139.8(5) 140.6(4) 138.7(5) 1149 (7) 191.8(9) 190.0( 12) 193.4( 10) 232.4(2) (6) 193(2) 194(2) 194(2) 232.3(5) 187.3( I I ) 189.6( 12) 1 97.1 ( I 0) 190.4(10) 195.2( 1 I ) 214.1 (10) 2 15.6(8) 208.1 ( I 0) 190(2) 193(2) 194(2) 190(2) 195(2) 215(2) 21 2(2) 207(2) 21 3(2) 214(2) 21 l ( 2 ) 114(2) 11 l(3) 113(3) 11 l(2) 1W2) 1 15(2) 1 lO(3) 1 15(3) 1 15(2) 114(2) 117(2) 21 1.9(8) 208.4 (9) 21 0.8(9) 113.5(11) 114.8(15) 112.8(12) 113.7(14) 114.4(15) 11 1.0(12) 1 13.7( 13) 112.3(14) 115.6( 13) 115.6(11) 116.6( 1.1) (6) 107.7(6) 97.8(6) 94.3( 5 ) 95.2(6) (7) 106.8(4) 97.8(3) 93.0(2) 92.5(3) 108.2(3) 102.1(2) 115.3(1) 87.2(3) 90.5(3) 151.8(3) 98.9(3) 97.6(3) 171.0(3) 110.2(4) 113.1(3) 17 1.4(3) 108.1( 3) 115.6(3) 137.2(8) 136.0(7) 1 4 1.9( 9) 136.9(7) 143.7(7) 139.4(7) 105.5(5) 97.7(5) 117.4( 1) 9 1.9( 6) 87.4(6) 148.8(5) 93.7(5) 97.9(4) 167.3(6) 105.5(5) 110.3(5) 171.8(7) 110.3(6) 113.6(7) 137.6(15) 14 1.4( 15) 141.8( 15) 136.8(15) 1 39.1 (1 5 ) 140.5( 1 5 ) 1150 Table 4.Crystallographic data for compounds (1)--(7) Crystal system ?iw group M b/A C I A a/" rl" P/" u p Z D,/g cm-' F(000) Centring 28 No.centring reflections 20 ljmi ts No. of unique reflections Obs. data [ I 3 30(1)] p/mm-' No. of parameters R R' G (weight) Goodness of fit R = (?I POI - IF,I l)/Wol R' = CCw(lF,I - lFF)2/WF,,12]* and goodness of fit = [Ew(lF,I - IFc1)2/(No - reflections and N = number of variables. Weighting scheme used of form w-' = [02(F) + gP]. Table 5. Atomic co-ordinates ( x lo4) for [RuCo,H(CO) ,(PMe,)] (1) 0.000 99 2.592 X 743( 1) 1293(2) 935(2) - 123(2) 1744(5) 453( 12) - 235( 13) 2 305( 14) 2 191(11) 1 342(13) 1252(13) - 1 240(13) -1 195(14) 2 640( 11) 168( 11) - 658( 14) 557( 14) 97( 17) 1701(23) 1 839(15) 1167(16) 1129(17) - 766( 18) -750(18) 1 979(17) 394(14) - 193(15) 2 683(20) 121q32) 1713(29) compounds] and the relationship between the hydride and phosphine positions was observed in each of the crystal structures.The average metal-metal bond distances are [Table 1 exclud- ing bonds of (4) because of mixed occupancy) Ru-Co 262.8 (range 256.4-266.7) Ru-Rh 273.7 (272.5-274.9) Ru(p-H)Rh z 2 500 2 916(3) 4 558(3) 3 358(3) 3 281(7) 33(19) 2 611(21) 2 080(20) 896( 17) 4 906(21) 6 872(19) 1 946(18) 4 157(21) 4 109(16) 1 364(16) 5 155(21) 963(22) 2 619(27) 2 264(33) 1697(23) 4 657(28) 5 957(27) 2 497(29) 3 887(26) 3 898(24) 2 161(22) 4 675(25) 3 774(37) 4 311(49) 2 125(36) (1) 663.07 Orthorhombic Pna2 17.145(8) 10.708( 5 ) 11.971(5) 90 90 90 2 198(2) 4 2.00 1 288 8-1 8 11 5-55 (3) 769.1 1 Triclinic P1 8.945(3) 11.455(5) 13.738(5) 110.35(3) 95.97(3) 73.45(3) 1265.1(9) 2 2.02 744 13-29 13 3-50 7 385 5 025 2.61 364 0.03 3 0.034 0.000 66 1.047 (2) 725.14 Triclinic P1 8.846(3) 11.260(3) 13.71 6( 5) 110.12(2) 95.21(2) 74.16(2) 1234.0(7) 2 1.95 708 8-26 12 5-50 4 356 3 568 2.69 316 0.058 0.067 2640 1040 3.01 145 0.054 0.052 0.00 1 1.131 Y 1444(2) 3 719(3) 2 354(3) 3 278(3) 5 622(7) 1 762(20) - 972(20) 92(22) 3 415(20) - 264(23) 3 225(21) 1973(19) 5 235(23) 2 579(19) 4 805( 18) 1619(22) 1684(25) 26(29) 577(3 5) 3 456(25) 286.9 CO-CO 251.6 (248.6-256.5) Co-Rh 264.4 (261.5- 267.9) and Rh-Rh 275.8 pm (272.2-28 1.9).Equatorial phos- phines in compounds (6) and (7) make the Rh(1)-Rh(2) and Rh(1)-Rh(3) bonds (which are trans to the phosphine) shorter with respect to the Rh(2)-Rh(3) bond whereas the axial phosphines in (1) and (2) seem to have no effect on the Ru-Co and Co-Co distances. The phosphine ligands cause asymmetry of the carbonyls which bridge a metal with a M-P bond and a metal without a M-P bond. In the RuCo compounds (1) and (2) the carbonyls CO(12) and CO(13) have stronger bonds to M(l) as evidenced by shorter M-C bonds and larger M(1)-C(l2)-O(l2) and M( 1)-C( 13)-O( 13) angles.The corresponding carbonyls in RuRh compounds (6) and (7) however have stronger bonds to metals M(2) and M(3) on grounds of the M-C bond distances. In the latter compounds there is no significant difference in the M-C-0 bond angles. This reflects the different influence of axial and equatorial phosphines. In both [RuCo,H(CO) 1(PPh3)2] and [RuRh,H(CO) l(PPh3)2],6 which have axial phosphines the bridging carbonyls have stronger bonds to metals with phosphines but the carbonyls CO(13) and CO(23) in (5) are relatively symmetrical according to the M-C-0 angles (Co-C and Rh-C bond lengths are naturally different). Bridging carbonyls are asymmetric also in [Rh,(CO) O(PPh3)2],1 ' 4-55 2 844 1733 2.76 270 0.038 0.037 0.0005 1.100 where No = number of observed 766(3 1) 2 929(26) 2 473(26) 4 460(30) 2 841(28) 4 205(26) 2 096(24) 5 790(35) 6 540(49) 6 564(39) [CO,(CO)~ 1(PPh3)],'3 and [CO,(CO)~~{P(OCH~)~}~].~~ This reflects electronic differences between the carbonyl and phosphine ligands.The phenyl groups in the PMe,Ph derivatives (2) (3) and (7) are oriented so as to cap the hydride ligand. This implies that the steric demands of the hydride ligand cause the carbonyl coverage to open so as to make room for the phenyl group.14 In compound (7) the Ru(l)-Rh(l)-P(l)-C(41) (phenyl carbon) torsion angle is 13.1'. In (6) the corresponding Ru-Rh(1)- P-C(41) (methyl carbon) torsion angle is only -2.l0 showing the more symmetrical structure of (6).The axial phenyl groups are also orientated asymmetrically. The M(2)-M( l)-P-C and M(3)-M(l)-P-C torsion angles {C is the carbon which is nearest the M&H) hydride [phenyl carbon for (2) and (3) (4) 1 138.55 Monoclinic P2,lc 17.365(7) 21.109( 13) 13.303(6) 90 107.74(3) J. CHEM. SOC. DALTON TRANS. 1990 (7) 857.06 Triclinic P1 9.164( 5) 11.147(5) 1 4.3 56(9) 71.75(4) 82.58(5) 71.58(4) 1321(1) 2 2.15 816 15-22 11 (5) 1 171.51 Triclinic P1 13.079(6) 13.844(6) 14.118(5) 99.3 5(4) 103.61 (3) 102.05(4) 2 369(2) 2 1.64 1120 15-25 21 4-50 8 366 5 373 1.45 563 0.032 0.032 0.0005 1.031 90 4 645(4) 4 1.63 1744 9-26 11 4-45 6 259 2 118 1.48 279 0.052 0.062 0.0005 2.01 5 (6) 794.98 Orthorhombic Pna2 1 1.089(4) 11.887(6) 17.873(9) 90 90 90 2 356(2) 4 2.23 1504 14-22 15 4-55 6 059 3 571 2.47 316 0.039 0.039 0.0006 1.095 X z 1315(1) 2 183(1) 3 216(1) 1 820( 1) 2 955(2) -898(5) 901(6) 1606(7) 918(6) 3 536(6) 5 358(5) - 52(5) 2 441(7) 3 748(5) 451(5) 2 860(6) - 69(8) 1061(7) 1 500(7) 1415(6) 3 383(6) 4 535(6) 6W6) 2 218(7) 3 265(6) 1 142(6) 2 727(7) 3 463(6) 4 429(7) 4 816(9) J.CHEM. SOC. DALTON TRANS.1990 Table 6. Atomic co-ordinates ( x lo4) for [RuCo,H(CO) 1- Y 2 067( 1) 4 498( 1) 3 298(1) 3 832(1) 6 639(2) 3 523(1) 3 432( 1) 2 674( 1) 919(1) 3 166(2) 3 662(9) 1970(8) - 348(7) 995(8) 4 088(7) 847(7) 4 740( 7) 2 432( 10) 6 943(8) 6 090( 8) 4 284(9) 1665(8) - 307(9) 2 224( 7) 5 909( 8) 3 923(7) 5 170(7) 2 307(8) 1994(8) -2 014(9) 5 769(7) 1651(8) - 146(9) 3 612(11) 2 840(11) 531(9) 1389(8) 4 245(8) 1789(8) 4 221(8) 2 847(8) 5 677( 11) 5 061(10) 3 656(10) 2 041(9) 1 88( 10) -901(11) 5 143(9) 3 962(8) 4 748(7) 2 882(9) 7 603(7) 7 700(9) 4 556(9) 1918(9) 667(10) 1 197(9) 757( 1 1) - 68 1( 13) 8 431(11) 9 OlO(11) 8 953(12) 8 268(11) 7 088(9) 7 373(10) -1 746(14) -1 335(15) 149( 12) 4 454( 1 1) 3 681(13) 4 220( 10) 3 285(10) 2 899(8) 4 056(7) 2 094(8) (PMe*Ph)I (2) and methyl carbon for (l)]) are -46.4 and 21.9 -50.5 and 14.5 and -43.5 and 24.9' for compounds (l) (2) and (3) re- spectively.Experimental Preparations of the compounds have been described pre- viously.'o Pure samples of (3) and (5) were obtained by t.1.c. on silica gel 60 F254 plates (Merck) using hexane-CH2C12 mixtures as eluants suitable crystals of (1-7) were grown from CH2C1,-hexane mixtures by slow evaporation at room temperature. Crystallography.-Details of crystal parameters data collec- tion parameters and refined data for complexes (1)-(7) are summarized in Table 4.Intensity measurements were made on a Nicolet R3m diffractometer using graphite-monochromatized carbon atoms were refined independently anisotropically in Mo-K radiation (a scan mode with scan width 1' from KaI2 (3) and isotropically in (4). Hydrogen atoms were placed at and scan speed 2.02-29.3' and on a Enraf-Nonius CAD4 diffractometer using graphite- width 0.80 + 0.35 tan6 and scan speed 1 - 16.5" min-') for monochromatized Mo-K radiation (a - 26 scan mode scan (4). All data sets were corrected for Lorentz and polarization factors. Empirical absorption corrections were made from y-scan data for (1)-(3) and ( 5 H 7 ) and for (4) as described by Walker and Stuart." For (1) and (6) the values of R R' and the goodness of fit for the two alternative absolute structures are presented in Tables 5-1 1 respectively.were effectively the same. Additional material available from the Cambridge Crystallo- graphic Data Centre comprises H-atom co-ordinates thermal parameters and remaining bond lengths and angles. min-') for ( 1 H 3 ) and (5)-(7) Structure analysis and refinement. The crystal structures were determined by direct methods and subsequent Fourier synthesis X Y z 2 059( 1) 4 562(1) 3 425( 1) 3 962( 1) 6 782( 1) 1911(4) 3 452( 1) 3 514(1) 2 604( 1) 847( 1) 3 204( 1) 3 756(5) 1 363( 1) 2 210(1) 3 304(1) 1 834(1) 2 971(1) -861(3) -416(4) 957(4) 4 028(5) 881(3) 4 622(4) 2 219(4) 2 424(5) 6 929(4) 6 259(5) 4 093(5) 1 694(4) -217(4) 787(3) 1628(3) 879(3) 3 429(3) 5 484(3) - 25(3) 2 328(3) 3 876(3) 340(3) 2 891(3) - 28(3) 1 OlO(3) -2 091(4) 5 771(4) 1 636(4) -261(4) 3 633(5) 2 793(5) 6 013(4) 3 857(4) 5 062(4) 2 523(4) 1 980(4) 501(4) 5 634(6) 5 246(5) 3 553(6) 2 030(5) 274(5) -952(5) 1 363(4) 4 241(5) 1831(4) 4 209(4) 2 846(4) 5 256(5) 1 528(4) 1 393(4) 3 268(3) 4 639(3) 693(3) 2 160(4) 3 926(4) 4 738(4) 3 052(4) 7 700(4) 7 714(5) 8 390(6) 4 620(5) 1 816(5) 582(5) 1 261(5) 836(6) -648(7) 3 414(3) 1 060(3) 2 757(3) 3 478(3) 4 427(4) 4 817(5) 4 248(6) 3 336(6) 2 918(4) 4 058(4) 2 072(4) 2 957(41) 8 999(6) 8 987(7) 8 346(6) 7 281(5) 7 502(5) 4 745(52) - 1 729(7) - 1 341(8) 145(7) 4 495(6) 3 592(7) 1 867(62) 1151 Table 7.Atomic co-ordinates ( x lo4) for [RuCo,RhH(CO) (PMe,Ph)l (3) using the SDP program packageI6 for compound (4) and SHELXTL l 7 for the others. Cobalt atoms were distinguished from the second-row transition metals crystallographically [for compound (4) mixed occupancies were observed]. Compounds contain second-row metals both in the apical site and in at least one of the basal sites. The apical metal in each of the compounds was deduced to be ruthenium from 'H n.m.r. ~pectra.~? lo Metal phosphorus oxygen and carbon atoms (3-7) were refined anisotropically except in (l) where only isotropic refinement was possible for oxygen and carbon atoms due to the low-reflection-to-parameter ratio (small crystal).The phenyl rings were refined as rigid groups with individual isotropic thermal parameters except in (3) and (4) where also the phenyl calculated positions with fixed isotropic thermal parameters except in (3) where they were refined isotropically. The hydride ligand could be located only in (3) and (5) from final difference maps and was found to bridge the basal metal atom face as indicated also by 'H n.m.r. results." In (4) the metal atom sites M(l) and M(2) are disordered being occupied by Rh and Co with population parameters 0.75 0.5 for Rh and 0.25 0.5 for Co respectively. The final atomic co-ordinates for compounds (1-7) 1152 Table 8.Atomic co-ordinates for [RuCo .,5Rh,.,,H(CO),,(PPh,),] (4) X 0.712 6(1) 0.709 8( 1) 0.801 4( 1) 0.646 4( 1) 0.696 l(3) 0.880 2( 3) 0.576 l(9) 0.737 3(9) 0.835 4(8) 0.710 l(8) 0.9 12 O(8) 0.545 7(9) 0.554 5(8) 0.889 l(7) 0.529 7(7) 0.731 7(8) 0.630( 1) 0.727( 1) 0.789( 1) 0.706( 1) 0.867( 1) 0.593( 1) 0.592( 1) 0.830(1) 0.597( 1) 0.729( 1) 0.774( 1) 0.754( 1) 0.8 16( 1) 0.894( 1) 0.91 3( 1) X 1 770(1) 1 603( 1) 132( 1) 140(1) 3 086( 1) 2 740( 1) -1 061(5) -1 547(5) 1386(5) 1762(4) 1 509(5) - 2 115(4) - 302(6) 3 380(3) 25(4) - 392(4) - 627(6) - 917(6) 930(6) 1756(5) 1518(5) -1 171(6) - 113(6) 2 706( 5) 422(5) 157(5) 3 399(5) 4 447(5) 4 630(7) 3 777(7) Table 9.Atomic co-ordinates ( x lo4) for [RuCoRh,H(CO),,(PPh,)~] (5) O.O05( 1) 0.3 50(2) 0.254( 1) 0.427( 1) 0.431(1) 0.253( 1) 0.115(2) 0.010( 1) 0.339( 1) 0.223( 1) 0.076( 1) 0.414( 1) 0.498( 1) 0.58 5( 2) 0.586(2) 0.502( 1) Z 8 949( 1) 7 414(1) 8 527( 1) 7 277( 1) 9 341(1) 6 329( 1) 9 982(5) 7 444(5) 10 014(5) 11 072(3) 7 501(4) 7 100(5) 5 866(4) 9 386(3) 8 836(4) 5 563(3) 9 422(6) 7 835(6) 9 454(6) 10 276(5) 7 450(4) 7 301(6) 6 424( 5) 8 861(4) 8 497(5) 6 306(5) 10 652(4) 11 285(5) 12 282(5) 12 647(5) 12 029(5) 11 039(5) 2 731(6) 2 530(5) z 0.298 l(1) 0.301 7( 1) 0.205 3( 1) 0.125 l(2) 0.307 6(4) 0.1 18 5(3) 0.384( 1) 0.226( 1) 0.512(1) 0.521( 1) 0.287( 1) 0.089( 1) - 0.067( 1) 0.412 l(9) 0.230 8(9) Y 0.176 83(7) 0.049 04(7) 0.108 89(9) 0.108 5(1) - 0.060 2(2) 0.059 8(2) 0.205 O(7) 0.309 4(6) 0.191 2(6) 0.065 O(7) 0.214 8(6) 0.219 2(8) 0.045 l(6) 0.053 5(6) 0.066 O(6) 0.182 2(6) 0.194( 1) 0.259 4(9) 0.185 7(8) 0.059 8(9) 0.174 6(9) 0.177( 1) 0.071 8(9) 0.062 5(9) 0.068 l(8) 0.148 6(8) -0.096 8(8) -0.122 8(9) -0.149( 1) -0.148( 1) -0.121 3(9) Y 2 188(1) 3 214( 1) 3 148(1) 1 488(1) 1253(1) 3 258(1) 2 4oW) 4 120(5) 5 124(4) 2 906(4) 5 374(4) 1410(4) - #0(4) 4 288(3) 277(4) 2 466(4) 2 661(6) 3 753(6) 4 374(6) 2 631(5) 4 548(5) 1592(6) 323(6) 3 603(4) 921(5) 2 396(5) 1 159(4) 1 422(5) 1 347(6) 1012(6) 737(5) 808(5) Atom C(116) C(121) C( 122) C(123) C( 124) C( 125) C( 126) C(131) C(132) C(133) C( 134) C( 135) C( 136) C(211) C(212) C(213) C(214) C(215) C(216) C(22 1) C(222) C(223) C(224) C(225) C(226) C(23 1) C(232) C(233) C(234) C(235) C(236) Atom C(120) C(121) C( 122) C(123) C( 124) C(125) C( 130) C(131) C( 132) C( 133) C( 1 34) C(135) C(210) C(211) C(212) C(213) C(214) C(215) C(220) C(221) C(222) C(223) C(224) C(225) C(230) C(23 1) C(232) C(233) C(234) C(235) X 0.853( 1) 0.603( 1) 0.566( 1) 0.495(2) 0.459(2) 0.489(2) 0.564(1) 0.696( 1) 0.641( 1) 0.632( 1) 0.682( 1) 0.744(2) 0.748(2) 0.826 l(9) 0.757( 1) 0.709( 1) 0.738( 1) 0.806( 1) 0.854( 1) 0.962 9(9) 0.946( 1) 1.006( 1) 1.085( 1) 1.103( 1) 1.042( 1) 0.930( 1) 0.988( 1) 1.029( 1) 1.01 4( 1) 0.958( 1) 0.917(1) X 4 408(4) 4 883(5) 5 861(5) 6 392(5) 5 949(5) 4 961(5) 2 686(4) 2 149(6) 1859(6) 2 087(6) 2 609(6) 2 920(5) 2 OlO(5) 2 003(6) 1415(8) 855(7) 852(7) 1408(6) 3 906(5) 4 633(6) 5 557(7) 5 739(7) 5 028(9) 4 112(7) 3 324(5) 2 629(7) 3 038( 10) 4 084( 1 1) 4 776(9) 4 408(6) 1581(36) H(1) Z J.CHEM. SOC. DALTON TRANS. 1990 0.419( 1) 0.324( 1) 0.38 l(2) 0.405(2) 0.360(2) 0.295(2) 0.279(2) 0.190( 1) 0.095( 1) O.W( 1) 0.008(2) 0.089(2) 0.190(2) - 0.020( 1) -0.039( 1) -0.144( 1) -0.225( 1) - 0.206( 1) -0.201( 1) 0.108(1) 0.070( 1) 0.065( 1) 0.095( 1) 0.126( 1) 0.13 1( 1) 0.177(1) 0.278( 1) 0.325( 1) 0.274( 1) 0.175( 1) 0.128( 1) z 9 146(4) 8 558(5) 8 412(5) 8 853(6) 9 460(6) 9 599(5) 8 670(4) 7 656(5) 7 108(5) 7 571(6) 8 563(6) 9 125(5) 5 074(4) 4 218(5) 3 274(5) 3 185(6) 4 004(7) 4 953(5) 6 687(5) 7 608(5) 7 905(6) 7 270(7) 6 358(8) 6 044(6) 6 lOl(4) 5 862(5) 5 633(7) 5 652(8) 5 890(7) 6 llO(6) 7 603(33) Y -0.095 O(8) -0.084 2(9) - 0.053( 1) -0.071( 1) - 0.12 1 ( 1) -0.15 1( 1) -0.138( 1) -0.104 4(9) -0.090 2(9) -0.123 4(9) -0.169( 1) -0.186( 1) - 0.1 55( 1) 0.038 5(7) 0.003 5(8) -0.010 2(9) 0.010 5(8) 0.042 6(8) 0.059 7(8) 0.109 2(8) 0.172 O(9) 0.215 l(9) 0.191 4(9) 0.134 O(8) 0.090 9(8) -0.013 3(7) -0.010 9(8) - 0.064 6(9) -0.120 3(9) -0.124 2(9) - 0.070 O(8) Y 1769(4) 1210(5) 1 640(6) 2 633(6) 3 194(5) 2 780(5) - 71(4) -315(4) - 1 296(5) - 2 054(5) -1 832(5) - 854(4) 3 312(5) 2 674(5) 2 732(7) 3 436(8) 4 080(8) 4 016(7) 4 363(5) 4 579(6) 5 394(7) 6 004(7) 5 818(8) 4 995(6) 2 183(5) 1 220(5) 382(7) 496(9) 1 432(10) 2 301(7) 1905(34) J.CHEM. SOC. DALTON TRANS. 1990 Table 10. Atomicco-ordinates ( x lo4) for [RuRh,H(CO) l(PMe3)] (6) Y 1313(1) 2 644(1) 3 720(2) 2 293(2) - 603(4) 2 235( 14) 4 321(14) 340(14) 1513(14) 2 619(17) 2 913(16) 5 308( 16) 5 113(17) - 82( 14) 2 254( 12) 5 395(12) 2 276( 17) 3 606(17) 1 075(16) 1 433(13) 2 654( 18) 2 883(16) 4 714(15) 4 599(19) 795( 17) 2 351(16) 4 473( 18) - 1 318(27) - 690(25) - 1 636(20) X 3 635(1) 4 820(1) 3 673( 1) 4 713(1) 3 175(3) 3 999( 10) 5 792(8) 5 916(9) 2 821(8) 6 509(8) 6 547(11) 3 719(9) 2 534(12) 5 002(9) 2 410(8) 4 932(10) 4 273( 12) 5 389(12) 5 483( 1 1) 3 116(10) 5 898(10) 4 657( 1 1) 3 701(11) 2 957(12) 4 688(10) 2 913(11) 4 619( 10) 3 530(20) 2 201(15) 3 277(26) Acknowledgements The Academy of Finland is acknowledged for financial support.2 500 1773(2) 3 01 l(1) 4 036(2) 2 879(5) 6 385(11) 4 643(12) 4 261(14) 286(10) 1835(16) - 777( 12) 5 056(14) 1550(20) 1 566(12) 4 142(13) 2 129(12) 5 518(15) 4 409( 13) 4 176(15) 1 105(13) 1835(18) 173(16) 4 316(16) 2 091(20) 1 765(14) 3 566(15) 2 222(13) 4 061(33) 3 127(36) 1785(38) References 1 G. Wilkinson F. G. A. Stone and E. W. Abel ‘Comprehensive Organometallic Chemistry,’ Pergamon Oxford 1982 vol.4 p. 889; vol. 5 pp. 7 and 317; vol. 6 p. 763. 2 J. Pursiainen and T. A. Pakkanen J. Chem. SOC. Dalton Trans. 1989 2449. 3 E. Roland and H. Vahrenkamp Organometallics 1983,2 183. 4 J. Pursiainen and T. A. Pakkanen J. Organornet. Chem. 1989,362 375. 5 J. Pursiainen T. A. Pakkanen B. T. Heaton C. Seregni and R. J. Goodfellow J. Chem. SOC. Dalton Trans. 1986,681. 6 J. Pursiainen T. A. Pakkanen and J. Jaaskelainen J. Organomet. Chem. 1985,290,85. 7 S . Martinengo P. Chini V. G. Albano F. Cariati and T. Salvatori J Organomet. Chem. 1973,259,379. 8 M. Bojczuk B. T. Heaton S. Johnson C. A. Ghilardi and A. Orlandini J. Organomet. Chem. 1988,341,473. 9 T. A. Pakkanen J. Pursiainen T. Venalainen and T. T. Pakkanen J. Organomet. Chem. 1989,372,129. z Table 11. Atomic co-ordinates ( x lo4) for [RuRh,H(CO) 1- Y 8 491(1) 9 597( 1) 7 063( 1) 7 791(1) 11 839(2) 10 267(9) 6 024(8) 9 215(8) 9 382(9) 5 669(8) 5 586(10) 7 152(9) 7 280(9) 9 091(8) 10 708(6) 4 830(6) 9 602(10) 6 951(10) 8 945(9) 9 474(9) 6 189(9) 6 152(10) 7 390(9) 7 420(9) 8 736(9) 9 831(9) 5 939(8) 12 651(8) 13 222(11) 13 717(16) 13 696(19) 13 151(19) 12 613(13) 12 777(10) 12 278(10) X 1 655(1) 3 628( 1) 4 616(1) 2 332( 1) 3 281(3) - 1 619(9) 675(9) 1897(9) 6 033(8) 4 683( 10) 7 839(9) - 699(9) 3 335(10) 5 893( 10) 778(8) 3 567(8) -408( 11) 1 050( 10) 1 832(10) 5 118(10) 4 657( 11) 6 672( 11) 433( 11) 3 060( 10) 5 179(11) 1 686(10) 3 517(9) 1 530( 11) 165(12) -1 184(16) - 1 189(26) 1 18(29) 1 494(17) 3 163(14) 4 779( 12) 10 J. Pursiainen and T. A. Pakkanen Acta Chem. Scand. Ser. A 1989 43,463. 11 B. T. Heaton L. Longhetti D. M. P. Mingos C. E. Briant P. C. Minshall B. R. C. Theobald L. Garlaschelli and U. Sartorelli J. Organomet. Chem. 1981,213,333. 12 H. Matsuzaka T. Kodama Y. Uchida and M. Hidai Organo- metallics 1988,7 1608. 13 D. J. Darensbourg and M. J. Incorvia Inorg. Chem. 1981,20,1911. 14 L. J. Farrugia M. Green D. R. Hankey M. Murray A. G. Orpen and F. G. A. Stone J. Chem. SOC. Dalton Trans. 1985 2384; J. Pursiainen and T. A. Pakkanen J. Organomet. Chem. 1986,315 353. 15 N. Walker and D. Stuart Acta Crystallogr. Sect. A 1983,39 158. 16 SDP Structure Determination Package Enraf-Nonius Delft 1978. 17 SHELXTL Plus Release 3.4 Nicolet Instruments Corp. Madison Wisconsin 1988. Received 1 l t h May 1989; Paper 9/01983I 1153 z 2 221(1) 2 874( 1) 2 746( 1) 4 147(1) 2 135(2) 2 374(6) 2 509(6) - 22(5) 4 209(6) 1222(6) 3 582(7) 4 783(6) 6 230(6) 1 152(6) 4 097(5) 4 267(5) 2 307(7) 2 397(6) 804(7) 3 705(7) 1798(7) 3 299(7) 4 534(6) 5 456(7) 1851(7) 3 893(6) 3 927(6) 1455(7) 1881(9) 1403(16) 486( 18) - 5( 14) 508(9) 2 988(9) 1 266(9)

ISSN:1477-9226    

DOI:10.1039/DT9900001147

出版商:RSC    

年代:1990

数据来源: RSC