Joyce L. C. Chim

Heterobimetallic μ-nitrido complexes containing ruthenium(II) dithiocarbamate

Abstract Interaction of [Ru(Co)H(Et2dtc)with triflic acid (HOTf) afforded [Ru(Co)H(Et2dtc)(PPh3)2(OTf) (1), which has been characterized by X-ray crystallography. The RuC, RuO, average RuS and average RuP distances in 1 are 1.811(5), 2.216(3), 2.433 and 2.423 A, respectively. Reaction of 1 with amines L results in the formation of adducts trans-[Ru(CO)(Et2dtc)(PPh3)2L](OTf) (L=N2H4 (2) and NH2OH (3)). The RuC, RuN, average RuS and average RuP distance in 3 are 1.85(1), 2.179(8), 2.433 and 2.393, respectively; the RuNO angle being 119.7(5)°. Treatment of 1 with [NnBu4][OsN(C7H6S2)2] ([C7H6S2]2−=3,4-toluenedithiolate(2−)), and [ReN(Et2dtc)2] (Et2dtc=N,N-diethyldithiocarbamate) gave the corresponding μ-nitrido complexes [Ru(CO)(Et2dtc)(PPh3)2(NOsO3)] (4), [Ru(CO)(Et2dtc)(PPh3)2{NOs(C7H6S2)2}] (5) and [Ru(CO)(Et2dtc)(PPh3)2{NRe(Et2dtc)2}] (6). The structures of complexes 4–6 have been established by X-ray crystallography. The OsN and RuN distances, and OsNRu angle in 4 are 1.719(7) and 2.075(7) A, and 155.1(4)°, respectively. The OsN and RuN distances and OsNRu angle in 5 are 1.680(6) and 2.068(6) A, and 166.2(3)°, respectively. The ReN and RuN distances, and ReNRu angle for 6 are 1.670(3) and 2.108(3) A, and 170.9(2)°, respectively. The bond lengths and angles for these μ-nitrido complexes are indicative of asymmetric bridging mode of nitride, i.e. MN→Ru(II) (M=Os(VIII), Os(VI), Re(V)).

Heterobimetallic nitrido-bridged Ru(II)NOs(VIII) and Ru(II)NOs(VI) complexes containing ruthenium porphyrins

Abstract Treatment of Ru(por)(NO)(OTf) (por=dianion of 2,3,7,8,12,13,17,18-octaethylporphyrin H 2 (OEP) or 5,10,15,20-tetra( p -tolyl)porphyrin H 2 (TTP), OTf=triflate) with [N n Bu 4 ][OsO 3 N] afforded the nitrido-bridged Ru(II)–Os(VIII) complexes [(por)(NO)RuNOsO 3 ] (por=OEP ( 3 ) or TTP ( 4 )). The structure of 3 has been established by X-ray crystallography. The Ru–N(O), Ru–N(Os) and Os–N distances in 3 are 1.83(2), 2.03(1) and 1.79(1) A, respectively; the Ru–N–O and Ru–N–Os angles are 153(1) and 138.4(8)°, respectively. Reaction of Ru(por)(NO)(OTf) with [N n Bu 4 ][OsNL 2 ] (H 2 L=3,4-toluenedithiol) gave the nitrido-bridged Ru(II)–Os(VI) complexes (por)(NO)RuNOsL 2 (por=OEP ( 5 ), TTP ( 6 )). Treatment of Ru(OEP)(NO)(OTf) with ReN(Et 2 dtc) 2 (Et 2 dtc= N , N -diethyldithiocarbamate) afforded the Ru(II)–Re(V) complex (OEP)(NO)RuNRe(Et 2 dtc) 2 (OTf) ( 7 ). Complexes 3 and 4 exhibit porphyrin-centered oxidation along with Os(VIII)–Os(VII) and Ru(II)–Ru(I) reductions. Complexes 5 and 6 exhibit Os(VII)–Os(VI) and porphyrin ring oxidation along with Ru(II)–Ru(I) reduction.

Tosylimido complexes of tungsten(VI)

Abstract Treatment of W(CO)6 with N,N-dichloro-p-toluenesulfonamide affords [W(NTs)2Cl2]x 1, which reacts with bipy (2,2′-bipyridine) to give the adduct W(NTs)2Cl2(bipy) 2. The average WN(imido), WCl and WN (bipy) distances are 1.782, 2.352 and 2.284 A, respectively. Reaction of [W(NTs)2Cl2]n with NaTp [Tp = hydrido(trispyrazolyl)boratel gives TpW(NTs)2Cl 4. These tungsten(VI) tosylimido complexes undergo imido transfer reactions with tertiary phosphine to give W(IV) and the N-tosyl phosphinimine.

Dimetallic gold(I) and platinum(II) complexes containing a trioxoosmium(VIII) moiety. Crystal structures of [Au(PPh3)(NOsO3)] and cis-[Pt(PMe3)2(NOsO3)2]

Reaction of [NBun4][OsO3N] with [Au(PPh3)(CF3SO3)] and cis-[Pt(PMe3)2(CF3SO3)2] afforded the dimetallic complexes [Au(PPh3)(NOsO3)] and cis-[Pt(PMe3)2(NOsO3)2], respectively, which have been characterised by X-ray crystallography.

Direct functionalisation of σ-aryl ligands: preparation of homoleptic functionalised aryls of osmium(IV)

The osmium(IV) tetraaryl complex [Os(C8H9)4] (C8H9 = 2,5-dimethylphenyl) reacts with pyridinium tribromide in the presence of Fe powder to give [Os(C8H8Br)4], which undergoes Suzuki coupling with arylboronic acids to afford a series of homoleptic functionalised aryls of osmium(IV).

Syntheses and crystal structures of bi- and tri-metallic complexes containing a trioxoosmium(VIII) moiety

Interaction of cis-[Pt(dppm) 2 (O 3 SCF 3 ) 2 ] [dppm = bis(diphenylphosphino)methane], cis-[Pt(Bupy)(O 3 SCF 3 ) 2 ] (Bupy = 4-tert-butylpyridine), [Ir(CO)(PPh 3 ) 2 (O 3 SCF 3 )], and [Rh(cod)(OH 2 )(OTs)] (cod = cycloocta-1,5-diene, OTs = tosylate) with [NBu n 4 ][NOsO 3 ] afforded bimetallic nitrido-bridged complexes cis-[Pt(dppm)(NOsO 3 ) 2 ] 3, trans-[Pt(Bupy) 2 (NOsO 3 ) 2 ] 4, [Ir(CO)(PPh 3 ) 2 (NOsO 3 )] 5 and [{Rh(cod)(NOsO 3 )} 2 ] 6, respectively. Complex 4 crystallises in the P space group with a = 7.936(1), b = 10.758(2), c = 7.738(1) A, α = 100.02(1), β = 99.75(1), γ = 101.75(1)°, U = 622.5(2) A 3 for Z = 1. The Pt–N (Os), Os–N and the mean Os–O distances are 1.958(7), 1.681(7) and 1.724 A, respectively. Complex 5 crystallises in the P2 1 /n space group with a = 10.124(1), b = 15.564(2), c = 22.623(3) A, β = 100.08(2)°, U = 3509.7(7) A 3 for Z = 4. The Ir–N, Os–N and the mean Os–O distances are 1.998(7), 1.710(7) and 1.718 A, respectively. Treatment of [Au(PPh 3 )(NOsO 3 )] 1 with Ph 3 PNPh gave the N-phosphinimine complex [Au(PPh 3 ){N(PPh 3 )Ph}][NOsO 3 ] 7. Complex 7 crystallises in the P2 1 /n space group with a = 8.780(1), b = 20.781(2), c = 20.711(5) A, β = 91.23(1)°, U = 3788.0(9) A 3 for Z = 4. The Au–N distance is 2.091(8) A and the C–N–P angle in the phosphinimine is 127.0(7)°. Reaction of 1 with Bupy led to substitution of Bupy for [NOsO 3 ] and formation of [Au(PPh 3 )(Bupy)][NOsO 3 ] 8. Reaction of [Pt(dppf)(O 3 SCF 3 )Cl] [dppf = 1,1′-bis(diphenylphosphino)ferrocene] with [NBu n 4 ][NOsO 3 ] afforded the trimetallic complex [Pt(dppf)(NOsO 3 )Cl] 11. Complex 11 crystallizes in the P2 1 /c space group with a = 20.058(2), b = 14.899(1), c = 23.949(2) A, β = 114.57(2)°, U = 6508(1) A 3 for Z = 8. The mean Pt–N, Os–N and Os–O distances are 2.06, 1.66 and 1.67 A, respectively.