J. CHEM. SOC. DALTON TRANS. 1994 1571Synthesis, Structure and Relative Hydrolytic Stability ofcis-[PtCI,L] and cis-[W(CO),L] where L is the BidentateTriaminophosphine Ligand [MeNCH,CH,N( Me)PN( Me)CH,],*John Powell, Alan Lough and Michael RasoDepartment of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, M5S 1A 1, Canadar I I 1 The ligand MeNCH,CH,N(Me)PN(Me)CH,CH,N(Me)PN(Me)CH,CH,NMe (L) reacted with [{Pt-(C,H,)CI,},] to give a mixture of cis-[PtCI,L] and trans- [{PtCI,(p-L)},] and with [W(CO),(nbd)](nbd = norbornadiene) to give cis-[W(CO),L] and [{W(CO),(p-L)},] (n = 2 4 ) . The ligand L and[W(CO),L] are readily hydrolysed to give HP0,2-, 2MeNHCH,CH,NH,Me+ and MeNHCH,CH,NHMe.In contrast the complex [PtCI,L] is considerably more resistant to ligand hydrolysis.The molecularstructures of cis-[PtCI,L], cis-[W(CO),L] and [W(CO),(MeNHCH,CH,NHMe)] {a hydrolysis productof the reaction of [W(CO),L] with water} have been determined by single-crystal X-ray diffractionstudies. Crystal data (all monoclinic): cis-[PtCI,L], space group Cc, a = 17.986(2), b = 9.286(1), c =12.059(1) A, j3 = 91.07(1)", Z = 4, R = 0.024 (R' = 0.028); cis-[W(CO)L], space group Pn, a =15.61 l(3). b = 8.437(2), c = 27.604(6), j3 = 99.78(3)", Z = 6, R = 0.036 (R' = 0.039); [W(CO),-(MeNHCH,CH,NHMe], space group C2/c, a = 22.960(2), b = 7.456(1), c = 14.039(1) A, p =106.60(1)", Z = 8, R = 0.040 (R' = 0.045).Metal complexes of chelating bidentate tertiary phosphineligands have been extensively studied for the last 25 years.Recently several groups have turned their attention to thechemical properties of metal complexes of bi- and multi-dentatephosphite ligands. 1-3 There is however very little publishedwork relating to complexes of corresponding bidentate tri-aminophosphine ligands.This may be, in part, because of theknown susceptibility of the P-N bond to undergo hydr~lysis.~In this paper we report the synthesis of the bidentatetriaminophosphine ligand [MeNCH,CH,N(Me)PN(Me)-CH,], (L) and the synthesis and structures of thecomplexes [PtCI,L] and m(CO),L]. Whilst free L andco-ordinated L in m(CO),L] are easily hydrolysed, thecomplex [PtCI,L] is considerably more resistant to ligandhydrolysis.r 1Results and DiscussionThe compound L was obtained from the reaction of PCl, withN,N'-dimethylethane-1,2-diamine in dry benzene in thepresence of triethylamine [equation (l)].Removal of2 PCI, + 6 MeNHCH2CH2NHMe + 6 NEt3 -mEt,H]Cl by filtration and the solvent in uacuo gave L as awhite crystalline solid which was used in subsequent reactionswithout further purification.The platinum compound cis-EtCl,L] 1 was obtained fromthe addition of L to the stoichiometrically required amount of[(Pt(C,H,)Cl,},] [equation (2)]. Monitoring of the crude* Supplementary data available: see Instructions for Authors, J. Chem.SOC., Dalton Trans., 1994, Issue 1, pp. xxiii-xxviii.reaction product, which was pale yellow, by ,lP-(lH} NMRspectroscopy indicated the presence of cis-[PtCl,L] 1 [S(31P)64.6, 1J(195Pt-31P) 4967 Hz] and a second complex which isprobably the trans-dimeric complex [CI,Pt(p-L),PtCI,] 2[S("P) 21.3, 1J(195Pt-31P) 2432 Hz].On standing in polarsolvents 2 isomerizes to the monomeric complex 1 whichrecrystallizes from dichloromethane as white prisms.The tungsten complex w(CO),L] 3 was obtained bytreating L with w(CO),(nbd)] (nbd = norbornadiene) inrefluxing benzene for 48 h [equation (3)]. The infrared spectrumin the v(C0) region of the crude product is consistent with theformulation w(CO),L]. No absorptions associated withtri- or penta-carbonyl species were observed. However the31P-{1H) NMR spectrum of the crude product shows thepresence of 3 as the major product (cu. 75%) together with threeminor products (cu. 8% each) tentatively assigned as[(W(CO),L},] (n = 2 4; 3 5; or 4 6) in which L functions as abridging ligand. The complex cis-w(CO),L] was obtained asyellow prisms on recrystallization from CH2Cl,1572 J.CHEM. SOC. DALTON TRANS. 1994The molecular structure of [PtCl,L] 1 as determined bysingle-crystal X-ray diffraction is shown in Fig. 1. Bond lengthsand angles are listed in Table 1. As expected the immediateco-ordination geometries of the Pt atom and the six nitrogenatoms are close to planar with very slight deviations fromplanarity occurring for five of the six N atoms. The sum of theC-N-C and C-N-P angles varies from 346" for N(5) to 358" forN(1). Atom N(5) lies almost in the PtCl,P, plane and theC2N2P2Pt ring adopts a distorted boat configuration.The molecular structure of w(CO),L] as determined bysingle-crystal X-ray diffraction is shown in Fig. 2.There arethree molecules in the asymmetric unit. Bond lengths and anglesfor molecule A are given in Table 2. Molecules B and C havesimilar geometries. The complex exhibits the anticipatedoctahedral geometry at tungsten whilst the nitrogen atoms ofthe L ligand exhibit slight distortions from planar geometry.The sum of angles C-N-C and C-N-P varies from 349" forN(2) to 360" for N(6). The C2N,P,W ring adopts a distortedchair configuration.A question of concern with respect to pursuing further studiesof the co-ordination chemistry of the triaminophosphine L wasthe relative stability/reactivity of its complexes to hydrolyticcleavage of the P-N bonds.A qualitative assessment of thehydrolytic stabilities of 2 and 3 has been obtained bymonitoring the 31P-{1H} NMR spectra of these complexes inCH,Cl,-MeCN in the presence of a small amount of addedwater at 20 "C. Solutions were ca. 0.02 mol dm-3 in complex andwater was added in a ca. 50-fold excess. The 31P-{1H} NMRspectrum of the initially formed platinum complex indicated thepresence of cis-[PtCl,L] 1 as the major solution speciestogether with the trans dimer 2. Within 1 h the signal of the transcomplex had disappeared and the only signal observable wasthat of the cis complex 1. This observation is consistent with atrans dimer to cis monomer isomerization in the relatively polarCH,Cl,-MeCN-water medium. The resulting spectrumremained unchanged after 7 d at 20 "C indicating that nohydrolysis of the P-N bonds had taken place.In contrast thetungsten complex [W(CO),L] 3 and the presumed oligomers4-6 are hydrolytically unstable. A 31P-{1H} NMR study of amixture of complexes 3-6 in CH,Cl,-MeCN-water at 20 "Cshows that concurrent with the loss of the signals of thesecomplexes a new signal assignable to a tungsten intermediate isobserved at 6 101 with J(183W-3'P) = 280 Hz. This peakreaches a maximum intensity after ca. 2 h reaction time and thendisappears. A plausible structure for this intermediate is theanionic complex [W(CO),{ [MeNCH,CH,N(Me)bO],H}] - 7which is structurally analogous to the known compound[NEt3H][Mo(CO),((PPh,0),H)1.5 Throughout the reactiona peak at 6 4 grows in and represents the sole phosphorus-containing product at the end of the reaction.The chemical shiftand the observed J('H-31P) of 558 Hz are consistent with thisspecies being the expected hydrolysis product HP03, - .6 UponFig. 1 Two views of the molecular structure of [PtCl,L] 1Table 1 Bond lengths (A) and angles (") for [PtCl,L] 12.378(3)2.230(3)1.663( 11)1.686(8)1.662( 10)1.460( 17)1.472( 17)1.477( 14)1.434( 15)1.448( 14)1.452( 15)1.5 1 O(20)1 $52 1 ( 1 5)87.4( 1)169.1 (1)89.5(1)110.5(4)94.4(5)106.3(5)114.3(4)92.4(5)112.1(6)112.5(9)120.8( 1 1)1 22.3( 8)I 1 1.4(8)118.8(10)123.0(8)1 17.6(7)2.365(3)2.228(3)1.680( 11)1.685( 1 1)1.654( 12)1.41 9( 17)1.438( 17)1.41 3( 16)1.455( 17)1.468( 14)1.465( 17)1.499( 18)85.0( 1)177.0( 1 )98.0( 1)120.2(4)107.4(5)12 1.4(4)112.1(4)102.8(5)125.1(9)1 1 1.9(8)1 17.0( 10)124.7(8)112.9(8)119.9(9)116.6(7)1 15.4(3)11 1.9(9) P(2)-N(6)-C(lO) 122.9(8)120.4(8) C(lO)-N(6)-C(12) 116.4(10)107.3( 1 1) N(2)-C(2)-C( 1) 105.9( 10)106.0(9) N(4)-C(6)-C(5) 104.0(9)113.1(9) N(6)-C( 10)-C(9) 1 1 1.5(9)completion of the reaction a yellow crystalline material hadformed in the NMR tube.It was identified as [W(CO),-(MeNHCH,CH,NHMe)] 8 by single-crystal X-ray diffractionJ. CHEM. SOC. DALTON TRANS. 1994 1573Table 2 Bond lengths (A) and angles (") for LW(CO),L] 3W( 1 A)-P( 1 A)W( 1 A)-C( 1 A)W( 1 A)-C(3A)P( 1 A)-N( 1 A)P( 1 A)-N( 5A)P( 2A)-N(4A )O( 1 A)-C( 1 A)O( 3A)-C( 3 A )P( 1 A)-W( 1 A)-P(2A)P(2A)-W( 1 A)-C( 1 A)P(2A)-W( 1 A)-C(2A)P( 1 A)-W( 1 A)-C(3A)C( 1 A)-W( I A)-C(3A)P( 1 A)-W( 1 A)-C(4A)C( 1 A)-W( 1 A)-C(4A)C(3A)-W( 1 A)-C(4A)W( 1 A)-P( 1 A)-N(2A)W( 1 A)-P( 1 A)-N(5A)N(2A)-P( lA)-N(SA)W( 1 A)-P( 2A)-N(4A)W( 1 A)-P(2A)-N(6A)N(4A)-P(2A)-N(6A)2.5 16(4)1.934( 17)2.011(16)1.686(16)1.687(13)1.669( 13)1.186(25)1.156(21)104.0( 1)1 7 1 .1 (5)85.4(5)92.1(5)88.2(7)93.0( 5)92.6(7)174.9(7)113.8(5)119.6(5)108.4(7)114.4(5)109.7(7)1 17.7(5)W( 1 A)-P(2A)W( lA)-C(2A)W( 1 A)-C(4A)P( 1 A)-N(2A)P(2A)-N(3A)P(2A)-N(6A)O( 2A)-C( 2A)P( 1 A)-W( 1 A)-C( 1 A)C( 1 A)-W( 1 AFC(2A)P(2A)-W( 1 A)-C(3A)C(2A)-W( 1 AFC(3A)P(2A)-W( lA)-C(4A)C(2A)-W( lA)-C(4A)W( 1 A)-P( 1 A)-N( 1 A)O( 4A)-C( 4A)P( 1 A)-W( 1 A)-C(2A)N( 1 A)-P( 1 A)-N(2A)N( 1 A)-P( 1 A)-N(5A)W( lA)-P(2A)-N(3A)N(3A)-P(2A)-N(4A)N(3A)-P(2A)-N(6A)P( 1 A)-N( 1 A)<( 5A)2.525(4)1.976( 17)2.01 7( 16)1.724( 14)1.683( 14)1.642(14)1.144(21)1.162(20)84.1(5)170.2(5)86.3(7)88.2( 5)8 5.7(7)90.4(5)89.3( 7)1 17.0(5)92.5(7)101.7(7)118.1(5)90.7(7)10237)113.2(12)N( 1 A)-C(5A)N(2A)-C(6A)N( 3A)-C( 7A)N(4A)-C(8A)N(5A)-C( 13A)N(6A)-C( 14A)C(13A)-C(14A)C(5A)-C(6A)1.458(27)1.384(29)1.477(20)1.400(26)1.498(23)1.505(21)1.534(3 1)1.50 l(25)124.8(14)112.5(12)116.7(16)1 2 1.4( 1 2)114.8(12)117.5(15)122.0( 1 1)120.3u 1)N( 1A)-C(9A) 1.372(24)N(2A)-C( 1 OA) 1.399(25)N(3A)-C( 1 1A) 1.457(22)N(4A)-C( 12A) 1.455(24)N(SA)-C( 15A) 1.424(2 1)N(6A)-C( 16A) 1.41 5(26)C(7A)-C(8A) 1.468(25)P( 1A)-N( lA)-C(9A)P( 1 A)-N(2A)-C(6A)C(6A)-N(2A)-C( 10A)P(2A)-N(3A)-C(llA)P(2A)-N(4A)-C(8A)P( 1 A)-N( 5A)-C( 15A)P(2A)-N(6A)-C( 14A)C(8A)-N(4A)-C( 12A)C( 14A)-N(6A)-C( 16A) 1 14.0( 13) 177.4( 14)W(lA)-C(2Ab0(2A) 117.1(13) W(lA>-C(3A)-0(3A) 173.1(16)W(IA)-C(4A)-0(4A) 177.7(17) N(lA)-C(SA)-C(6A) 105.6(18)N(2A)-C(6A)-C(5A) 108.7(19) N(3A)-C(7A)-C(8A) 103.9(14)N(4A)-C(8A)-C(7A) 107.5(16) N(SA)-C(13A)-C(14A) 11 1.3(14)N(6A)-C( 14A)-C( 1 3A) 1 1 1.9( 13)W( lA)-C( 1 A)-O( 1 A)C(SA)-N(IA)-C(9A) 117.5(17)P( lA)-N(2A)-C( 1 OA) 1 20.2( 13)P(2A)-N(3A jC(7A) 11 1.7(9)C(7A)-N(3A)-C(I 1A) 118.3(13)P( 1 A)-N(SA)-C( 13A) 1 1 6 4 10)C(13A)-N(5A)-C( 15A) 1 14.1( 13)P(2A)-N(4A)-C( 12A) 1 23.0( 12)P(2A jN(6A)-C( 16A) 125.7( 12)Fig.2 The molecular structure of [W(CO),L] 3n-N, ,N- -JP-" \The molecular structure is shown in Fig. 3 and bond lengths andangles are given in Table 3.For comparison purposes the hydrolysis of compound Lunder similar conditions to that of [W(CO),L] was alsoinvestigated. Initial hydrolysis of free L is essentially complete inca. 20 min. Four new signals of similar magnitude andexhibiting one-bond 1J(31P-'H) spin-spin coupling wereobserved at 6(31P) 11.1 [1J(31P-1H) = 5651, 10.3 (556), 4.0(558, HP032-) and -4.0 (648 Hz). After 24 h HP03,- is thefinal hydrolysis product. The intermediate hydrolysis productswere not structurally identified.In conclusion the reaction of the bidentate triaminophosphineL with tungsten carbonyl and platinum chloro complexes hasbeen investigated with a view to assessing the hydrolyticstability of L when co-ordinated to a transition metal.Theplatinum and tungsten complexes [PtCI,L] and w(CO),L]exhibit markedly different reactivities with L being rapidlyhydrolysed when co-ordinated to Wo whilst at 20 "C [PtCl,L]Table 3CH,NHMe)] 8Bond lengths (A) and angles (") for [W(CO),(MeNHCH,-2.297(8) W-N(2) 2.308( 11)1.947( 10) w-C(2) 1.986( 12)2.01 7( 10) w-C(4) 2.023(9)0(2)-C(2) 1.141 (1 6) 1.181( 13)1.1 52(13) 0 ( 4 >- c ( 4 1 1.142( 12)1.5 1 1( 16) N( 1 )-C(7) 1.487( 18)1.495( 14)1.483( 18)1.477( 17) N(2tC(8)N(l)-W-N(2) 76.5(3)N(2)-W-C(1) 97.0(4)N(2)-W-C(2) 172.3(4)N( 1)-W-C(3) 92.7(4)C(1)-W-C(3) 87.8(4)N(I)-W-C(4) 91.2(3)C(1)-W-C(4) 88.7(4)C(3)-W-C(4) 175.5(4)W-N(l)-C(7) 108.7(7)W-N(2)-C(6) 115.6(8)C(6)-N(2)-C(8) 109.7( 8)W-C(2)-0(2) 179.6( 10)W-C(4)-0(4) 175.2(10)N(2)-C(8)-C(7) 110.3(9)N(1)-W-C(1) 173.4(4)N(1)-W-C(2) 95.9(4)C(l)-W-C(2) 90.7(5)N(2)-W-C(3) 91.2(4)C(2)-W-C(3) 88.9(5)N(2)-W-C(4) 92.1(4)C(2)-W-C(4) 88.3(4)W-N(lbC(5) 114.1(6)C(5)-N(l)-C(7) 11 1.3(8)W-N(2)-C(8) 107.6(8)W-C( 1 )-O( 1) 177.1(9)W-C(3)-0(3) 175.4(10)N(l)-C(7)-C(8) 108.0(9)is essentially inert with no evidence of hydrolysis after 7 d.Thisdifference in reactivity is possibly a reflection of the relativedegree of positive charge residing on the P atoms in the twocomplexes and/or the ease with which the respective metals canaccommodate negative charge in an intermediate such as 9.Theproposed intermediate is structurally analogous to the recentlyreported iron complex 11 which was obtained via nucleophilicdisplacement of phenoxy groups from the co-ordinatedP(OPh), ligand of 10 [see equation (4)].7 The results obtainedIFe' +C</ 'P(OPh)3O O10 11574 J. CHEM. soc. DALTON TRANS. 1994Table 4 Crystal data, details of intensity measurements and least-squares parametersEmpirical formulaCrystal colour/habitCrystal size/mmMrCrystal class 3" groupb/ACIAP/"UlA3zDJg cm-jp(Mo-Ka)/cm-'o Scan width/"Range 20 collected/"Absorption correctionMinimum, maximum transmission coefficientsTotal no.reflectionsNo. unique reflectionsNo. observed data [F > 3o(F)]Weighting gRR'Goodness of fitLargest and mean A/oParameters refinedMaximimum, minimum density in A F maple A-'F ( o wRint1Colourless, block0.15 x 0.15 x 0.10586.3MonoclinicCC17.986(2)9.286( 1)12.059( 1)91.07( 1)20 1 3.7(7)41.93473.9911441-10 + 0.60 tan 05.652.0Semiempirical0.373,0.485225420890.00019010.00030.0240.0280.960.13, 0.022080.76, 0.51C12H30C12N6P2Pt3Yellow, needle0.30 x 0.15 x 0.10616.3MonoclinicPn15.61 l(3)8.437(2)27.604(6)99.78(3)3544.9( 13)61.73250.5618240.52 + 0.57 tan 0Semiempirical0.347, 0.799853575730.00054380.00030.0360.0391.260.00, 0.005431.09,O.OOC16H30N604P2W4.3-54.08Yellow, needle0.2 x 0.15 x 0.1382.0Monoclinic22.960(2)7.456(1)14.039( 1)106.60( 1)2303.2(3)82.203100.2714240.82 + 0.55 tan 0Semiempirical0.1 1 1,0.606285623710.03619000.00000.0400.0452.530.00, 0.00I371.41, -1.14C13H10N204W4c2/c6.1-54.0O(3)Fig.3 The molecular structure of ~(CO),(MeNHCH,CH,NH-Me11 8suggest that the rate of hydrolysis of co-ordinated bidentatetriaminophosphines may be tuned by appropriate choice ofmetal, oxidation state and complementary ligands. Furtherstudies of the chemistry of co-ordinated L and structurallyrelated ligands are in progress.ExperimentalProton NMR spectra were recorded on a Varian Gemini 200,31P-(1H} NMR spectra on a Varian Gemini 300 spectrometer.All 'H NMR spectra were recorded in CDCl, solution andreferenced to SiMe,, ,'P-{ 'H} spectra in CDCl3 and referencedto H$O4.The IR spectra were recorded on a Nicolet 5DXFourier-transform spectrometer using 0.5 mm NaCl solutioncells. All reactions (unless otherwise specified) were done undera nitrogen atmosphere using dry degassed solvents. Thecomplexes [{Pt(C,H4)C12)?] and [W(CO),(nbd)] wereprepared as reported in the literature.Table 5 Atomic coordinates for [PtC12L] 1X Atom Y z0.133 300.232 5(2)0.059 O(2)0.210 l(2)0.036 5(2)0.228 4(6)0.299 9(6)-0.016 5(5)- 0.036 2(5)0.178 6(4)0.061 l(5)0.307 9(7)0.348 9(6)0.177 7(8)0.322 8(7)- 0.095 9(6)-0.097 9(6)- 0.029 9(8)0.002 6(7)0.178 O(6)0.137 3(6)0.203 6(7)0.006 9(7)0.020 8(3)-0.123 5(3)- 0.189 8(3)0.205 l(3)0.144 9(3)0.222 l(12)0.193 2(12)0.220 2( 13)0.063 l(10)0.366 8(8)0.262 6( 12)0.236 4( 18)0.172 7( 15)0.192 O(14)0.128 3(15)0.185 5(16)0.049 l(12)0.345 7( 13)0.394 6( 11)0.279 4( 12)0.492 8( 1 1)0.366 3( 15)-0.033 l(14)0.879 600.951 2(3)0.880 5(3)0.910 9(3)0.813 l(3)1.045 9(9)0.876 O(9)0.911 l(8)0.753 8(9)0.867 l(7)0.71 7 6(9)1.070 4( 12)0.973 9(12)1.131 5(11)0.773 9( 1 1)0.893 2(10)0.826 7( 11)0.971 5( 10)0.659 l(12)0.749 O(9)0.681 9(9)0.931 2(14)0.673 O( 12)I t Preparations.-MeNCH,CH ,N(Me)PN(Me)CH,CH,N-(Me)PN(Me)CH,CH,NMe (L).To syn-N,N'-dimethylethane-1 ,Zdiamine (25 cm3) in benzene (600 cm3) was added PCl, (1 5.4cm3) in benzene (15 cm'). Then triethylamine (67.45 cm3) wasadded quickly and the reaction allowed to stir for 2 h. Theprecipitate of [NEt,H]Cl was filtered off and washed withbenzene (2 x 75 cm3). Removal of the solvent from the filtrateand washings gave the required product L as a moisture-sensitive white crystalline solid. Yield 52%. The 'H NMRspectrum in CDCI, showed two doublets at 6 2.42 [J(,'P-'H)= 14.41 and 2.54 (1 2.0 Hz) in the expected 6 : 12 ratio assignableI J. CHEM. SOC. DALTON TRANS. 1994 1575Table 6 Atomic coordinates for w(CO),L] 3X1 .o0.987 4(2)1.099 7(3)0.869 l(10)0.984 6(8)0.835 9(9)1.159 9(8)0.973 3(10)0.889 3(8)1.158 l(7)1.048 7(10)1.067 6(8)1.173 2(9)0.91 7 4( 10)0.992 6( 10)0.898 9( 11)1.102 6( 1 1)0.888 l(13)0.853 6(16)1.1 19 2(10)1.079 O( 13)1.017 6(13)0.875 8(13)1.204 7( 12)1.004 9( 14)1.111 3(11)1.180 6(10)1.067 7( 1 1)1.233 2(12)0.959 56(5)0.875 l(2)1.018 O(2)1.060 9(8)0.903 4(10)0.800 9(8)1.130 7(8)0.926 8(8)0.788 9(7)1.122 7(7)1.045 8( 10)0.834 5(7)0.955 7(8)1.022 6(12)0.924 8( 10)Y0.933 04(6)0.711 7(5)0.819 2(5)1.1094(18)1.232 3( 13)0.811 3(18)1.091 8(16)0.766 6( 17)0.61 1 9(18)0.948 O( 15)0.752 3(16)0.574 9( 15)0.688 4(17)1.042 l(19)1.122 9(20)0.848 l(21)1.033 5(20)0.724 O(24)0.591 6(28)0.971 8(20)0.816 6(22)0.888 l(23)0.488 3(24)1.081 4(23)0.597 9(24)0.524 5(21)0.641 4(21)0.455 3(19)0.609 8(24)0.780 51(6)1.007 O(5)0.898 l(5)0.469 9(14)0.598 3(15)0.637 7(16)0.901 l(15)1.089 3( 15)0.957 9(16)0.961 8(18)0.778 l(17)1.155 9(14)1.032 2( 15)0.587 O(22)0.666 9(20)Z1 .o1.060 3(2)0.945 5(2)1.055 3(7)0.931 3(5)0.925 9(7)1.070 2(6)1.117 2(5)1.049 2(5)0.917 4(5)0.891 2(5)1.072 8(5)0.969 8(5)1.033 3(6)0.956 7(6)0.951 9(7)1.043 8(6)1.128 l(8)1.091 3(9)0.865 3(6)0.850 4(8)1.144 O(8)1.014 5(7)0.943 9(7)0.885 l(8)1.030 9(7)1.023 O(6)1.109 6(6)0.944 9(7)0.670 95(3)0.700 5(2)0.599 2(2)0.649 7(5)0.760 2(5)0.598 3(5)0.740 3(5)0.754 l(5)0.724 8(5)0.614 l(6)0.556 3(6)0.660 2(5)0.566 O(5)0.655 8(7)0.726 6(7)X0.856 2(10)1.066 8(9)0.869 3(11)0.803 2(13)1.181 9(12)1.137 2(11)0.991 4(11)0.724 5( 1 1)1.146 5(12)0.987 7(13)0.881 4(12)0.872 3(10)0.777 8(12)0.983 l(13)0.484 74(5)0.606 0(2)0.381 l(2)0.343 8(8)0.593 8(9)0.401 6(8)0.669 2(8)0.693 2(7)0.374 3(10)0.273 l(8)0.577 3(7)0.386 O(7)0.552 7(9)0.397 7(10)0.551 5(11)0.431 l(11)0.753 8(10)0.775 2(9)0.283 8(12)0.236 O( 14)0.631 9(12)0.695 8( 11)0.434 5( 14)0.237 3(12)0.486 9(9)0.465 8( 11)0.641 5(10)0.324 6(11)0.590 l(8) -Y0.693 3( 19)0.863 6(19)1.109 5(22)0.977 8(26)0.895 2(23)0.739 8(22)1.210 O(20)0.844 l(23)1.108 3(23)0.656 3(26)1.199 l(21)1.083 9(20)1.275 l(21)1.115 2(26)0.282 71(7)0.387 6(4)0.516 3(5)0.113 9(14)0.399 7(16)0.143 2(18)0.255 9( 15)0.455 4(14)0.588 l(18)0.474 l(17)0.516 3(15)0.670 l(13)0.083 4( 18)0.178 8(18)0.363 l(22)0.198 8(21)0.233 5(19)0.388 9( 18)0.605 3(25)0.489 3(30)0.120 7(23)0.604 8(20)0.701 6(26)0.361 2(25)0.578 6(19)0.701 9(19)0.603 7(20)0.803 2(21)-0.033 l(12)z0.625 l(6)0.713 5(6)0.788 5(7)0.777 7(8)0.585 3(7)0.563 7(8)0.752 4(7)0.704 6(7)0.637 5(7)0.533 9(8)0.619 9(7)0.578 8(6)0.673 4(7)0.524 8(7)0.814 05(3)0.877 4(2)0.796 7(2)0.809 9(5)0.735 6(5)0.734 O ( 5 )0.901 l(5)0.914 3(5)0.855 6(5)0.740 4(5)0.786 4(5)0.916 6(5)0.837 6(5)0.81 3 2(6)0.762 9(6)0.762 5(7)0.868 6(7)0.900 l(7)0.879 l(6)0.714 l(8)0.736 9(8)0.935 2(7)0.830 9(7)0.727 5(9)0.819 O(8)0.91 1 O(6)0.870 6(6)0.951 8(6)0.827 9(7)Table 7 Atomic coordinates for w(CO),(MeNHCH,CH,NHMe)] 8X Y0.375 14(2) 0.199 51(5)0.448 3(4)0.307 8(4) 0.147 7(12)0.481 2(5) 0.387 9(14)0.328 4(4) 0.464 8( 10)0.418 O(5) 0.273 O( 12)0.332 2(5) 0.166 8(13)0.442 7(5) 0.325 5( 14)0.308 l(5) 0.057 O( 12)0.317 6(6) 0.588 3(15)0.424 l(6) 0.123 7(19)0.364 7(7) 0.554 9(14)0.380 3(5) 0.419 O(16)- 0.154 8( 10)0.269 6(4) - 0.029 4( 10)0.419 4(5) -0.023 6(14)z0.966 15(3)1.033 O(7)1.128 9(6)1.130 7(7)0.824 O(6)0.905 O(7)0.841 3(6)1.006 l(8)1.069 3(8)1.068 l(8)0.871 7(8)0.983 6(9)0.775 7(9)0.846 5(8)0.780 7(8)to the NMe groups, together with multiplets at 6 2.95 and 3.20assignable to the CH, protons; 6(3'P) 114 (s)."[PtCl,L] 1.A solution of L (0.725 g) in CH,Cl, (10 cm3) wasslowly added to [{Pt(C,H,)Cl,},] (0.66 g) in CH,CI, (50 cm3).After 1 h removal of the solvent gave a pale yellow solid whichconsisted of a mixture of complexes 1 and 2. 31P-{ 'H} NMR: 1,6 64.6, J( 195Pt-3 'P) = 4967; 2,6 21.3, J( 195Pt-31 P) = 2432 Hz.Recrystallization from CH,Cl, by slow evaporation gave 1 aswhite prisms (72%, m.p. 166-167°C). 'H NMR: 6 2.47[J(31P-'H) 9.2, NMe (bridge)], 2.81 [J(31P-1H) 11 Hz, NMe(ring)] and 3.25-3.51 (broad overlapping multiplets, CH,)(Found: C, 25.30; H, 5.25; N, 14.00. Calc. fOrC1,H30Cl,N6P,Pt:C, 25.60; H, 5.15; N, 14.35%).w(CO),L] 3. A solution of L (1.56 g) in benzene (80 cm3)was slowly added to a refluxing solution of w(CO),(nbd)](1.72 g) in benzene (250 cm3).The reaction was refluxed for 48h. Removal of the solvent gave a yellow-green solid. IR[v(CO)region]: 2010m, 1901 (sh, br) and 1882vs (br) cm-'. The31P-{1H) NMR spectrum in CH,Cl, showed the presence offour products: 6 118 {J('83W-31P) 315, p(CO),L] 3}, 121360, [{W(CO)4(p-L)}3] 5 ) and 124.5 {J('83W-31P) 370 Hz,[ { W(CO)4(p-L)}4] 6 ) . Recrystallization from CH,Cl,-hexanevia slow evaporation gave [W(CO),L] as yellow prisms (42%yield, m.p. 170-171 "C). IR[v(CO) region]: 201Om, 1909s and1875vs cm-'. 'H NMR: 6 2.38 [J(31P-'H) 6.8, virtual triplet,NMe (bridge)], 2.67 [J(31P-1H) 11.5, virtual triplet, NMe(ring)], 3.18 [br m, NCH, (ring)] and 3.34 [J(31P-1H) 23Hz, virtual triplet, NCH, (bridge)] (Found: C, 31.50; H, 5.15;13.65%).{J('83W-31P) 290, [{W(CO)~(P-L)}J 41, 124 {J(183W-31P)N, 13.35.Cak. for C ~ ~ H ~ O N ~ O ~ P ~ W : C, 31.20; H, 4.90; N1576 J. CHEM. SOC. DALTON TRANS. 1994Hydrolysis Experiments.-A 0.02 mol dm-3 solution ( 5 cm3)of [PtCl,L], [W(CO),L] or L in CH,Cl,-MeCN (9: 1 v/v) wasplaced in a NMR tube (diameter 5 mm) and water (1 cm3)added. The sample was monitored by 31P-{1H} NMRspectroscopy.X-Ray Structural Determinations.-Intensity data for com-pounds 1, 3 and 8 were collected on an Enraf-Nonius CAD-4diffractometer at room temperature, using graphite-mono-chromated Mo-Ka radiation (h = 0.71073 A). The o-scantechnique was applied with variable scan speeds.Intensities ofthree standard reflections measured every 2 h, for each crystal,showed negligible variation. For all compounds the heavy-atompositions were solved by Patterson methods and the locations ofall non-hydrogen atoms were determined from subsequentFourier difference syntheses. In each case all non-hydrogenatoms were refined with anisotropic thermal parameters (exceptfor 3 where carbon atoms were refined with isotropic thermalparameters) by full-matrix least squares to minimize Cw(Fo -FC)’, where w-l = 02(Fo) + gFo2. Hydro en atoms werethe refinement as riding atoms with general thermal parametersforeachstructure [0.105(10)for 1,0.0800for3and0.073(12) A3for 81. Crystal data, data collection, and least-squaresparameters are listed in Table 4. All calculations were performedusing SHELXTL PC” on a 486-66 personal computer.Relevant bond angles and distances are given in Tables 1-3 andatomic coordinates in Tables 5-7.Additional material available from the Cambridge Crystallo-positioned on geometric grounds (C-H 0.96 R ) and included ingraphic Data Centre comprises H-atom coordinates, thermalparameters and remaining bond lengths and angles.AcknowledgementsWe thank the Natural Sciences and Engineering ResearchCouncil of Canada for financial support.References1 M. J. Baker, K. N. Harrison, A. G. Orpen, P. G. Pringle and G. Shaw,2 T. J. Kwok and D. J. Wink, Orgunometallics, 1993, 12, 1954.3 M. J. Baker and P. G. Pringle, J. Chem. SOC., Chem. Commun., 1993,4 H. Goldwhite, Introduction to Phosphorus Chemistry, Cambridge5 G. M. Gray and C. S. Kraihanzel, J. Organomet. Chem., 1978, 146,6 J. R. Parks, J. Am. Chem. SOC., 1957,78,757.7 H. Nakazawa, K. Kubo and K. Miyoshi, J. Am. Chem. Soc., 1993,8 J. Chatt and M. L. Searle, Inorg. Synth., 1968, 17, 210.9 R. B. King and A. Fronzaglic, Inorg. Chem., 1966,5, 1837.J. Chem. SOC., Chem. Commun., 1991,803.3 14.University Press, Cambridge, 198 1, p. 12.23.115, 5863.10 F. Ramirez, A. V. Patwardham, H. J. Kayler and C. P. Smith,1 1 G. M. Sheldrick, SHELXTL PC, Siemens Analytical X-ray Instru-J. Am. Chem. SOC., 1967,89,6276.ments Inc., Madison, WI, 1990.Receiued 10th Nouember 1993; Paper 3/06738