摘要:
J. CHEM. SOC. DALTON TRANS. 1992 1417Disproportionation of a Ruthenium(ii1) Nitro Complex of aMacrocyclic Tertiary Amine in an Aqueous Medium tKwok-Yin Wong,a Chi-Ming Che,*ea Wai-Hing Yip,b Ru-Ji Wangb and Thomas C. W. Mak*rba Department of Chemistry, University of Hong Kong, Pokfutam Road, Hong KongDepartment of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong KongThe reaction of trans- [RuLCI,] + (L = 1,5,9,13-tetramethyI-l ,5,9,13-tetraazacyclohexadecane) withNO2- in water at 60 "C leads to the formation of trans-[RuL(O)CI]+ and tran~-[RuL(OH)(N0)]~+. Theformation of the products can be rationalized by the disproportionation of trans- [RuL(CI) (NO,)] +. Thestructures of the products have been determined by X-ray crystallography: trans- [RuL(O)CI] CIO,, spacegroup Pna2, (no.33), a = 12.616(1), b = 15.421 (3), c = 11.292(3) A; Ru=O and Ru-CI 1.75(1) and2.435(6) A; trans-[R~L(0H)(NO)J[C10,]~, space group Pbca (no. 61), a = 20.459(3), b = 29.16(1),c = 25.1 3(1) A; average Ru-OH and Ru-NO 1.906(9) and 1.74(1) A.The study of metal nitro complexes is of considerable interestbecause of the multiple-electron interconversion between M-NO, and M-NH3.1 Although a variety of transition-metal nitrocomplexes have been studied, the chemistry of ruthenium(n1)nitro complexes remains relatively ~nexplored.~.~" It has beensuggested that this class of compounds are unstable and wouldundergo rapid disprop~rtionation.~.~ Recently, Mukaida andco-workers reported the synthesis of a monooxoruthenium(1v)complex by oxidation of nitrosylruthenium(I1) with NaOC1.Their results suggested that the Ru"'-NO, species undergoesdisproportionation to give RuIV=O and Ru"-NO+.In orderfurther to investigate the chemistry of Ru"*-NO, complexeswith macrocyclic tertiary amine ligands we have attempted toprepare Ru"'-N02 by substitution of the C1- ligand in trans-[RuLC12] + (L = 1,5,9,13-tetrarnethyl-l,5,9,13-tetraazacyclo-hexadecane) with NO2-. The products of the reaction wereidentified by X-ray crystallography as trans-[RuL(O)Cl] + andtrans- [R u L( 0 H)( NO)] + .ExperimentalPhysical Measurements.-The UV/VIS absorption spectrawere recorded on a Milton Roy (Spectronic 3000 Array) diode-array spectrophotometer, infrared spectra as Nujol mulls ona Nicolet 20FXC FT-IR spectrophotometer, and 'H NMRspectra on a JEOL 270 MHz FT-NMR spectrometer.Elemental analyses were performed at National TaiwanUniversity.Preparation of trans-[RuL(O)Cl]ClO, and trans-[RuL(OH)-(NO)][CIO,],.-The complex trans-[RuLCl,]Cl was preparedas described previ~usly.~ Other chemicals were obtained asreagent grade and used without further purification.A mixture of trans-[RuLCl,]Cl (0.5 g) and NaNO, (0.1 g) indeionized water was warmed at 60 "C for 20 min.The colour ofthe solution changed from yellow to greenish blue. Uponcooling to 30 "C, NaClO, (ca. 1 g) was added to cause immediateprecipitation of blue crystalline trans-[RuL(0)C1]C104 (yieldca. 0.13 g) which was filtered off. The filtrate was left to stand inair. Yellow crystals of trans-[R~L(0H)(NO)][Cl0~]~ (yield ca.0.19 g) were obtained after about 1 d.Both complexes could bet Supplementary data available: see Instructions for Authors, J. Chem.SOC., Dalton Trans., 1992, Issue 1, pp. xx-xxv.recrystallized from hot water, although the quality of thecrystals of the 0x0 complex was poor. trans-[RuL(O)Cl]-ClO,: IR, v(Ru=O) 840 cm-'; UV/VIS (CH,CN), h/nm (&/dm3mol-' cm-'): 570 (160), ca. 360 (250) and 295 (1600) (Found: C,35.6; H, 6.8; N, 10.3. Calc.: C, 35.8; H, 6.7; N, 10.4%). truns-[RuL(OH)(NO)][ClO,],: IR, v(N0) 1825 cm-'; UV/VIS(water), h/nm (&/dm3 mot-' cm-'): ca. 375 (340), 320 (1OOO) and244 (26 300); 'H NMR (CD,CN), 6 2.12-2.4 (m, CH,), 2.76,2.8(s, NCH,) and 3.1-3.6 (m, NCH,) (Found: C, 30.2; H, 6.0 N,10.9.Calc.: C, 30.4; H, 5.85; N, 11.1%).X-Ray Structure Determination.-Details of crystal param-eters, data collection and structure refinement are given in Table1. Raw intensities collected were processed with the profile-fitting procedures of Diamond s and corrected for absorptionusing y-scan data.6 For trans-[RuL(O)Cl]ClO,, the L ligandexhibits slight configurational disorder and distance con-straints of 1.48(2), 1.52(2) and 1.54(2) A were applied to theN-C(methylene), N-C(methy1) and C-C bonds, respectively. Inaddition, two major orientations of the C10,- group wereidentified with half site occupancy assigned to the oxygenatoms, and distance constraints of 1.44(2) and 2.35(2) A appliedto the C1-0 bonds and 0 0 separations, respectively. Re-finement proceeded with isotropic thermal parameters for the Catoms and anisotropic ones for the remaining non-hydrogenatoms in the asymmetric unit.The H atoms were generatedgeometrically (C-H 0.96 A) and included in structure-factorcalculations with fixed isotropic thermal parameters. Reversalof the polarity of the structure produced no significantimprovement. Table 2 lists the atomic coordinates for the non-hydrogen atoms of trans-[RuL(0)C1]C104, Table 3 selectedbond distances and angles.The asymmetric unit in trans-[R~L(0H)(NO)][Cl0~]~ con-tains three independent RuN,O co-ordination polyhedra. Oneof the three L ligands exhibits two-fold disorder, which wasmodelled by two sets of atoms: N(12)-N(15) plus C(33)-C(48)and N(12')-N(15') plus C(33')4(48'), each of half site occu-pancy.Distance constraints of 1.48(2), 1.52(2) and 1.54(2) Awere applied to the N-C(methylene), N-C(methy1) and C-Cbonds in order to overcome correlation problems caused byoverlapping atoms. The non-hydrogen atoms except those ofthe disordered L ligand were subjected to anisotropic blocked-matrix refinement. The H atoms belonging to the hydroxideand disordered L ligand were not included in structure-factorcalculations, whereas the others were generated geometricall1418 J. CHEM. SOC. DALTON TRANS. 1992Table 1 Data collection and processing parameters for * trans-[RuL(0)C1]C104 and 1rans-[RuL(0H)(NO)][C10~],Molecular formulaMColour and habitSpace group4blA4UlA3ZF ( 0 WD,/g ~ m - ~Standard reflectionsIntensity variation (%)Rin, (from merging of equiv. reflections)p/cm-'Crystal size/mmMean prTransmission factorsScan type and rateScan rangeCollection rangeUnique data measuredObs.data with IFoI 2 60(lF01), nNo. of variables, pWeighting scheme, wR = ZI!Fol - l ~ c l p l ~ o ls =- C W l F O I - l~cl)2/(n 7 P)lfR' = C W I F O I - l ~ c l ~ 2 1 ~ w l ~ o 1 2 1 *Residual extrema in final differencemap/e A-jtrans- [ R u L( O)Cl] C10,C16H36C12N405Ru536.53Blue platePna2, (No. 33)12.61 6( 1)15.421(3)1 1.292(3)2196.9(7)411121.622+6KO349.780.04 x 0.34 x 0.420.130.154-0.563w28,2.49-15.63" min-'0.60" below Kal to 0.70" above Ka2h,k,l; 28,,, = 50"205 113092080.097(112), (120)[l - exp( -6 sin' 8/h2)]/[02(Fo) + 0.0010~Fo~2]0.1071.752 + 3.42 to - 2.011rans-C RuL( OH)( NO)] [ C104121 CiH 3 i'C12N 5O 1 0632.48Yellow polyhedronPbcu (No.61)20.459( 3)29.16( 1)25.13(1)14 992(10)2478481.68 1( o w , (641)+ 2KO808.870.28 x 0.32 x 0.340.1210.6860.709w, 3.01-15.63" min-I0.65" below Kal to 0.65" above Ka2h,k,l; 28,,, = 45"13 16960796830.072[l - exp( - 8 sin' 8/h2)]/[02(Fo) + 0.0008~Fo12]0.0861.338 + 1.42 to -0.62* Details in common: crystal system orthorhombic, graphite-monochromatized Mo-Ka radiation (h = 0.710 73 A); stationary counts for one-fifth ofscan time at each end of scan range.PFig. 1 A perspective view and atom numbering of the truns-[RuL(O)Cl] + cationand assigned the same isotropic thermal parameter U = 0.12A2.All computations were performed using the SHELXTL-PLUS program package' on a DEC microVAX-11 computer.Analytical expressions of atomic scattering factors were em-ployed, and anomalous dispersion corrections were incorpor-ated.' Tables 4 and 5 list the atomic coordinates of thenon-hydrogen atoms and selected bond distances respectivelyof trans-[RuL(OH)(NO)] [C104] ,.Additional material available from the Cambridge Crystal-lographic Data Centre comprises H-atom coordinates, thermalparameters and remaining bond lengths and angles.Results and DiscussionThe formation of Ru"=O and Ru"-NO+ complexes fromRu"'-N02 has previously been suggested.,' In this workthe reaction of trans-[RuLCl,] + with NaNO, gave similarproducts instead of the desired trans-[RuL(NO,),] +.TheUV/VIS spectrum of trans-[RuL(O)Cl) + is similar to those ofthe Ru'"=O complexes of tmc (tmc = 1,4,8,1 l-tetramethyl-1,4,8,11 -tetraazacycl~tetradecane),~ which have been reportedpreviously. Since trans-[RuL(O)Cl] + is paramagnetic its 'HNMR spectrum has not been recorded. According to Schreineret ruthenium nitrosyl complexes such as trans-[Ru-(NH,),(OH)(NO)]CI, and [Ru(NH,),(NO)]Cl, should beformulated as [Ru"-NO+] species. A direct comparison be-tween trans-[RuL(OH)(NO)I2+ and trans-[Ru(NH,),(OH)-(NO)],' revealed that their UV/VIS spectra and v(N0)stretching frequencies { v(N0) 1834 cm-' for trans-[Ru-(NH3)4(OH)(NO)]2 + ref.10) are similar, thereby suggestingthey may have similar electronic configurations. Assignment ofa co-ordinated OH - group in trans-[RuL(OH)(NO)I2 + basedon the short average Ru-O(0H) distance of 1.906(9) A isdiscussed in a later section. The 'H NMR spectrum of trans-[RuL(OH)(N0)I2+ in CD3CN exhibits two peaks at 6 2.8 and2.76 with unequal intensities, and two sets ofmultiplets at 6 3.1-3.6 and 2.12-2.4. The two peaks at 6 2.8 and 2.76 are assigned toNCH, protons. The multiplets at 6 3.1-3.6 are due to NCH,protons.The reaction of rrans-[RuLCl,]+ with NaNO, can befollowed by measuring the UV/VIS spectrum periodically. Apeak at A, 570 nm characteristic of trans-[RuL(O)Cl] +appeared in the early stages of the reaction.The formation oftrans-[RuL(O)Cl] + could not be due to aerial oxidation oftruns-[R~L(OH)(0H,)]~ + as the related trans- [RuL'(OH)-(0H,)l2 + (L' = macrocyclic tertiary amine ligands) complexeswere found to be stable under similar reaction conditionsJ. CHEM. SOC. DALTON TRANS. 1992Table 2 Atomic coordinates ( x lo4) for trans-[RuL(O)Cl]ClO,X8 393(1)10 230(4)7 075(11)502( 5 )466(20)1421(15)755(20)- 109(20)- 104(17)-538(13)869( 19)1 269(18)8 741(13)8 820( 18)8 058(13)8 01 l(14)9 665( 17)9 151(21)8 421(20)8 126(22)8 397(21)8 685(19)8 445( 18)7 913(18)8 337(19)8 574(19)8 480(21)9 128(23)7 731(18)9 955(20)6 910(14)6 826( 15)Y8 617(1)9 099(4)8 264(10)6 381(4)6 51 l(20)6 042(16)5 839(15)5 707( 13)5 922(16)6 726(17)7 177(12)7 062( 14)7 667( 11)7 481(20)9 475(13)9 705(13)7 097(17)6 421(17)6 698( 18)7 630(19)8 334(14)9 215(16)10 374( 13)10 821(16)10 584(14)9 735(15)8 892( 15)8 145(20)7 328(20)7 486(23)9 466( 16)9 768(19)Z7 5007 566( 14)7 570(20)2 552(11)1511(17)1 369(14)2 266(22)3 380(19)3 439( 17)2 833(21)3 046(22)2 628(24)6 057( 15)8 754(21)9 088( 16)6 310(16)6 273(24)7 106(20)8 136(21)9 786(21)10 686(21)10 140(20)9 018(19)7 968( 15)6 732( 19)5 171(18)4 450(22)4 993(23)5 496(24)9 219(26)9 448(22)6 075(24)* Disordered oxygen atoms of perchlorate anion were treated as O(2)-O(5) and 0(2't0(5'), each of half site occupancy.Table 3 Selected bond lengths (A) and angles (")[RuL(O)Cl]CIO,Ru-Cl( 1 ) 2.435(6) Ru-O( 1)Ru-N( 1 ) 2.23(2) Ru-N(2)Ru-N(~) 2.27(2) R U-N (4)C1( l)-Ru-O( 1)O(1)-Ru-N( 1)O( l)-Ru-N(2)C1( I)-Ru-N(3)N( l)-Ru-N(3)C1( l)-Ru-N(4)N( 1 )-Ru-N(4)N(3)-Ru-N(4)175.7( 8) Cl(l)-Ru-N(l)90.9(8) C1( 1 )-R u-N(2)87.6(8) N( l)-Ru-N(2)88.6(3) O( l)-Ru-N(3)174.6(6) N(2)-Ru-N(3)89.7( 5 ) O(l)-Ru-N(4)95.6(6) N( 2)-R U-N( 4)89.8(7)for trans-1.75(1)2.32(3)2.20(2)92.0( 5)89.5(6)84.5(8)88.2(8)90.1(8)93.2( 7)179.1(7)Meyer ' and Mukaida 3c and their co-workers proposed thetransfer of an oxygen atom from one Ru"'-N02 group toanother to give the intermediate [ClRu-N(0)O-N(0)-0-RuC1l2 + which easily decomposes into [CI-RU"-NO+]~ + and[O=RU'~-CI] +.It is likely that a similar mechanism operateshere.Structure of truns-[RuL(O)C1]C1O4.-Fig. 1 shows a per-spective drawing of the trans-[RuL(O)Cl] + cation. The Ruatom has distorted octahedral co-ordination comprising fournitrogen atoms of L and the chloro and 0x0 ligands which aretrans to each other. The Ru atom lies on the equatorial planecomposed of the four N atoms such that the mean deviation ofthe four N atoms from the plane is O.Ol(2) 8, and the Ru atom isdisplaced 0.003 A from it towards O( 1). The res ective Ru=Oclosely by values of 1.765(7) and 2.505(3) 8, in its analoguetrans-[Ru(tmc)O(Cl)]+. l 2 The configuration of the L ligand inand Ru-Cl bond lengths of 1.75(1) and 2.435(6) K are matched14190d0C(41)Fig.2 Perspective view and atom numbering of (a) cation I, (6)cation I1 and (c) the two-fold disordered cation 111 of trans-[RuL(OH)(NO)12 +. In (c), atoms representing one possible orientationof the L ligand are linked by solid lines and those representing the otherorientation by broken linesthe present complex is 'three up, one down', the same as intrans-[Ru(tmc)O(C1)] +, but different from the 'two up, twodown' configuration in trans-[RuLO2I2 + . I 3 The crystal struc-ture consists of a packing of discrete cations and anions withnormal van der Waals separations.Structure of trans-[RuL(OH)(NO)][C104],.-There arethree independent trans- [ R u L( OH)(NO)] + cations (labelled1-111) and six perchlorate anions in a crystallographic asym-metric unit of this complex. The co-ordination environmentabout each Ru atom can be described as a compresse1420 J.CHEM. SOC. DALTON TRANS. 1992Table 4 Atomic coordinates ( x lo4) for trans-[RuL(OH)(NO)][ClO,],Y Atom X Y z A426( 1)39(4)1 085(5)829(5)670(6)177(6)1 405(10)542( 13)- 5 14(5)1354(5)-272(12)-452( 10)1 474( 1)1997(3)709(4)1008(3)1 940(4)1282(4)1068(4)1705(4)2 015(8)1749(8)1 701(9)1252(8)9 119(1)9 450(4)8 609(5)8 814(4)8 438(4)8 724(5)9 832(4)9 513(5)8 397(8)7 911(8)7 855(8)8 137(7)- 748( 1 1)- 907( 10)-243(13)758( 12)1 180(11)1 259(10)1480(9)1719(10)379( 11)- 1 047(9)- 170(13)1930(8)831(8)755(7)674(9)859(9)1253(7)1718(7)2 198(6)2 259(7)2 409(7)1 609(8)1315(8)1441(7)8 841(9)9 714(11)9 437(9)10 053(9)10 371(7)10 113(7)9 412(9)8 834(8)8 471(8)8 824(9)10 264(8)9 407(9)Cation I1Ru(2) 4 662( 1)O(3) 4 696( 5 )O(4) 4 593(6)N(6) 4 640(6)N(7) 3 881(6)N(8) 5 442(6)N(9) 5 442(6)N( 10) 3 902(7)C( 17) 3 367( 13)C(18) 4 124(14)C( 19) 4 677( 12)C(20) 5 225( 13)9 006( 1) 973( 1)8 639(3) 1 602(3)9 584(3) 4x419 357(3) 4 19(4)8 560(5) 642(5)8 577(4) 616(5)9437(4) 1335(5)9 410(5) 1 407(5)8 459(10) 993(12)8 073(8) 583(11)8 018(7) 152(9)8 384(9) 115(10)6 033( 11)6 364( 10)5 996( 15)5 260( 14)4 667( 1 1)4 059( 12)3 250( 11)2 952(9)3 641(11)5 647( 10)5 558( 14)3 733(11)8 826(9)9 084(8)9 571(9)9 943( 1 1)10 007(8)9 903(8)9 390(9)8 957(8)8 674(9)8 173(7)9 357(10)9 237(9)474(10)1009(14)1 405(13)1792(9)1 464(10)1119(11)1034(9)126( 8)962(9)1893(7)1934(8)955(9)Disordered cation 111W 3 ) 7 152(1)O(5) 6 445(5)O(6) 8 220(8)NU 1) 7 824(6)N(12)* 6 829( 11)N(1 3) 6 619(12)NU4) 7 431(10)N(1 5 ) 7 684(8)C(33) 6 712(18)C(34) 6 217(18)C(35) 6 258(19)C(36) 6 632(16)C(37) 6 941(19)C(38) 6 975( 16)(339) 7 553(14)C(40) 8 082( 12)C(41) 8 052( 15)C(42) 7 653(16)C(43) 7 342( 13)C(W 7 325(17)C(45) 7 316(21)C(46) 5 891(14)6 266( 1)5 885(4)6 831(6)6 606(4)6 8 15(8)6 620(8)5 705(8)5 930(6)6 634( 17)7 067( 18)7 298(14)7 130(9)6 540( 12)6048(11)5 822(11)5 527( 11)5 219(10)5 419(8)5 967(9)6 463( 10)7 194(15)6 491(16)2 367( 1)2 575(4)2 061(7)2 203(5)2 908(9)1698(10)1 822(8)3 017(7)3 457( 12)2 796( 17)2 243(13)1 743(12)1 181(13)957(14)1252(9)1 994(11)2 493(10)2 959(12)3 536(9)3 751(15)3 022(21)1 707( 18)C(47)C(48)N( 12’)N( 13‘)N( 14’)N( 15’)C(33‘)C(34’)C(35‘)C(36‘)C(37’)C(38‘)C(39‘)C(40‘)C(41‘)C(42‘)C(43’)C(44‘)C(45‘)C(46’)C(47‘)C(48‘)6 948(16)8 389( 11)6 463( 13)7 021(13)7 849( 13)7 251(11)6 694( 17)6 356(26)6 210(22)6 372(16)6 977(19)7 634(20)7 629( 18)7 787(19)7 982(23)7 932( 14)7 267( 14)6 619(17)5 753( 15)7 521(20)8 554( 15)6 762( 19)5 307( 11)6 087( 1 1)6 840(9)6 055( 10)5 675(10)6 420(8)7 254(10)6 988(17)6 664( 13)6 151(13)5 566( 11)5 331(18)5 246( 13)5 806(12)6 327( 12)6 916(8)7 164(16)6 707( 15)6 196(18)5 807( 14)6 204( 16)5 441(12)1 822(15)3 051(12)2 280(11)1 532(11)2 511(10)3 225( 10)2 589(12)1 722( 13)1 256(18)1291(17)1381(19)1519(14)2 122(13)3 031(11)3 448( 18)3 407( 15)3 338(12)3 184(13)2 372( 17)1119(16)2 425( 17)3 600( 16)Perchlorate anionsCK 1) 3 174(2) 2 379(2) 5 125(2) CK2) 2 733(2) 1338(2)O(7) 3 061(9) 2 678(8) 4 747( 11) O(11) 3 034(8) 989(6)O(8) 3 795(8) 2 267(8) 5 037(10) O(12) 2 326(10) 1 087(7)O(9) 2 823(15) 2 412(12) 5 535(11) O(13) 3 149(12) 1598(6)O(10) 2 854(14) 2 015(10) 5 046(12) 0U4) 2 346(9) 1613(6)7 623(2)7 314(7)7 981(7)7 901(9)7 306(7)CK3) 683(2) 2 751(2) 6 726(2) Cl(4) 7 504(2) 114(2)O(15) 1284(10) 2 575(10) 6 720(14) 0U9) 7 206( 10) 267(6)O( 16) 616(11) 3 074(7) 7 116(8) O(20) 7 960(12) - 173(8)0U7) 269(9) 2 385(5) 6 806(6) O(2 1) 7 169(10) - 3( 10)O(18) 584(15) 2 923(7) 6 254(8) O(22) 7 850(13) 462( 10)5 009(2)5 468(7)5 130(8)4600(11)4 805(8)CK5) 5 061(3) 323(2) 3 401(2) CK6) 307(3) 1231(2)O(23) 5 645(13) 209(8) 3 541(13) O(27) 305( 12) 1097(7)O(24) 4 706( 1 1) 259(8) 3 849(7) O(28) -63(12) 1626(7)O(25) 4 771(16) 2(11) 3 133(9) O(29) 31(17) 941(7)O W ) 5 054( 11) 746(7) 3 222(11) O(30) 878( 14) 1 500(13)* The two-fold disordered ligand in cation I11 was treated as N(12w(48) and N(12’)-C(48’), each of half site occupancy.3 696(2)3 164(6)3 785(9)4 007(8)3 865(12J.CHEM. SOC. DALTON TRANS. 1992 1421Table 5 Selected bond lengths (A) and angles (") for trans-[RuL-(OH)(NO)l CCl0412Ru( 3)-O( 5 )Ru(3)-N(12)Rn(3)-N(14)R~(3)-N(12')Ru(3)-N( 14')O(6)-N( 11)O( 1)-Ru( 1)-N( 1)N( 1 )-Ru( 1)-N(2)N(l)-Ru( l)-N(3)O( l)-Ru( 1)-N(4)N(2)-Ru( 1)-N(4)O(l)-Ru(l)-N(S)1.909(9)2.24( 1)2.21( 1)1.14(2)1.9 lO(9)2.23(1)1.1 5( 2)1.90( 1)2.22(1)2.20(2)2.2 l(2)2.20(3)2.27(3)I. lO(2)176.6(4)91.8(4)90.9(4)88.8(4)175.1(4)85.4(4)Ru(3)-N( 1 1)Ru(3)-N( 13)Ru(3)-N( 15)Ru(3)-N(13')Ru(3)-N( 15')1.76( 1)2.23( 1)2.25(1)1.73( 1)2.24( 1)2.22( 1)1.74( 1)2.25(2)2.19(2)2.20(3)2.2 l(2)88.1(4)89.9(4)179( 1)86.6(4)92.1(4)octahedron with the hydroxide and nitrosyl ligands aligned inthe short axial direction.The Ru atom in each cation isdisplaced by 0.01( lW.07( 1) 81 from the mean plane of the fourequatorial N atoms towards the nitrosyl ligand. The Ru-N(macrocycle) bonds varying over a narrow range of 2.19-2.27 A[average 2.22(2) 813 are typical of those found in otherruthenium macrocyclic amine complexes.' 3*14 The Ru-0distances in the three cations are 1.909(9), 1.910(9) and 1.90(1) Arespectively, and the average length of 1.906(9) 81 is compar-able to that [1.910(3) 811 of the Ru-OH bond in frans-[Ru(~~)~(OH)(NO)]~+ (py = pyridine) 3d but shorter thanthose in tvans-[R~(NH~),(oH)(N0)]~+ (1.961 A)," Na2[Ru-(NO,),(OH)(NO)] (1.950 A) ' and [Ru(NO,),(NH,),(OH)-(NO)] (1.945 As in the case of trans-[Ru(NH,),(OH)-(N0)I2 + and tran~-[Ru(py)~(OH)(NO)]~ + the Ru-NO unit isessentially linear.The average RU-N(N0) distance is 1.74 81,which is comparable to those found in other ruthenium nitrosylcomplexes. The L ligands in the three cations exhibit differentconfigurations. As illustrated in Fig. 2, three N-methyl groupsare cis to the Ru-0 bond in cations I and I1 so that the L ligandassumes the 'three up, one down' configuration. On the otherhand, the two-fold disordered L ligand in cation 111 adoptsthe 'two up, two down' configuration [Fig. 2(c)]. The observeddisorder of cation I11 may be described in terms of two equallypopulated orientations related by an approximately 90"rotation about their common O-Ru-NO axis.The crystal structure consists of a packing of discrete cationsand anions with normal van der Waals separations exceptfor two short 0 0 distances [0( 1) O(8) 2.96(2) andO(3) O(17) 3.03(2) 813 which are indicative of hydrogenbonding between the hydroxyl ligand [0( 1) and 0(3)] and theoxygen atoms of the perchlorate groups [0(8) and 0(17)].AcknowledgementsWe acknowledge support from the University of Hong Kong,the Chinese University of Hong Kong and the Hong KongResearch Grants Council.C.-M. C. thanks the MicroanalyticalService Unit at the Chemistry Department of National TaiwanUniversity.References1 W. R. Murphy, jun., K. Takeuchi, M. H. Barley and T. J. Meyer,Inorg. Chem., 1986,25,1041; J. N. Armor and M. Z.Hoffman, Inorg.Chem., 1975,14,444.2 R. A. Leising and K. J. Takeuchi, J. Am. Chem. SOC., 1988,110,4079;L. F. Szczepura and K. J. Takeuchi, Znorg. Chem., 1990,29,1772.3 (a) H. Nagao, M. Mukaida, K. Shimizu, F. S. Howell and H.Kakihana, Inorg. Chem., 1986,25,4312; (b) H. Nagao, F. S. Howell,M. Mukaida and H. Kakihana, J. Chem. SOC., Chem. Commun., 1987,1618; (c) H. Nagao, H. Nishimura, Y. Kitanaka, F. S. Howell, M.Mukaida and H. Kakihana, Inorg. Chem., 1990, 29, 1693; ( d ) H.Nishimura, H. Matsuzawa, T. Togano, M. Mukaida, H. Kakihanaand F. Bottomley, J. Chem. Soc., Dalton Trans., 1990,137.4 C. M. Che, K. Y. Wong and C. K. Poon, Inorg. Chem., 1986,25,1809.5 R. Diamond, Acta Crystallogr., Sect. A, 1969,25,43.6 G. Kopfmann and R. Huber, Acta Crystallogr., Sect. A, 1968,24,348.7 G. M. Sheldrick, in Crystallographic Computing 3: Data Collection,Structure Determination, Proteins and Databases, eds. G. M.Sheldrick, C. Kruger and R. Goddard, Oxford University Press, NewYork, 1985, pp. 175189.8 International Tables for X-Ray Crystallography, Kynoch Press,Birmingham, 1974, vol. 4, pp. 55,99, 149.9 C. M. Che, T. F. Lai and K. Y. Wong, Inorg. Chem., 1987,26,2289.10 A. F. Schreiner, S. W. Lin, P. J. Hauser, E. A. Hopcus, D. J. Hamm11 F. R. Keene, D. J. Salmon, J. L. Walsh, H. D. Abruna and T. J. Meyer,12 C. M. Che, K. Y. Wong and T. C. W. Mak, J. Chem. Soc., Chem.13 T. C. W. Mak, C. M. Che and K. Y. Wong, J. Chem. SOC., Chem.14 D. D. Walker and H. Taube, Znorg. Chem., 1981,20,2828.15 S. H. Simonsen and M. H. Mueller, J. Znorg. Nucl. Chem., 1965, 27,16 T. S. Khodashova, V. S. Vergienko and M. A. Porai-Koshits,and J. D. Gunter, Inorg. Chem., 1972,11,880.Znorg. Chem., 1980,19, 1896.Commun., 1985,988.Commun., 1985,986.309.J. Struct. Chem., 1971, 12,439.Received 30th September 1991; Paper 1/05019
ISSN:1477-9226
DOI:10.1039/DT9920001417
出版商:RSC
年代:1992
数据来源: RSC