Anthony F. Hill

Diyne coordination chemistry: Reactions of [RuClH(CO)(PPh3)3] with diphenylbutadiyne and bis(phenylethynyl)mercury

Abstract The reaction of the hydridometal complex [RuClH(CO)(PPh3)3] with 1,4-diphenyl-butadi-1,3-yne has been investigated and found to proceed with monoinsertion to give a coordinatively unsaturated σ-vinyl complex [Ru-{C(Cue5fcCPh)ue5fbCHPh} Cl(CO)(PPh3)2], which is also the major product of the reaction of [RuClH(CO) (PPh3)3] with [Hg(Cue5fcCPh)2].

The coordination chemistry of 2,1,3-benzothiadiazole and 2,1,3-benzoselenadiazole. Complexes of ruthenium, osmium and iridium

Abstract The reactions of [MCl(C6H4Me-4)(CO)(PPh3)2] (M ue5fb Ru, Os) and [IrCl2H(PPh3)3] with 2,1,3-benzothiadiazole (BTD) result in quantitative formation of the adducts [MCl(C6H4Me-4)(CO)(PPh3)2(BTD)] and [IrCl2H(PPh3)2(BTD)], respectively. Similar reactions with 2,1,3-benzoselenadiazole (BSD) provide the corresponding selenium analogues. The thiocarbonyl complex [OsCl2(CS)(PPh3)2-(BSD)] is obtained by replacement of one phosphine in [OsCl2(CS)(PPh3)3]. The BSD and BTD ligands in the complexes are labile; [OsCl(C6H4Me-4)(CO)(PPh3)2-(BSD)] reacts with carbon monoxide and N,N-dimethylthionitrosamine to give [OsCl(C6H4Me-4)(CO)2(PPh3)2] and [OsCl(C6H4Me-4)(CO)(PPh3)2(SNNMe2)], respectively. The IR, 1H, and 31P-{1H} NMR data for the new complexes are reported and discussed.

The coordination chemistry of iminooxosulphuranes VI. Factors affecting coordination geometry in complexes of tosyliminooxosulphurane

Abstract The complexes [ML n (PPh 3 ) 2 (OSN-SO 2 C 6 H 4 Me-4)] (M = Ru, Rh, Os, Ir) have been prepared from the 16-electron complex [ML n (PPh 3 ) 2 ] or the corresponding tris(phosphine)compounds [ML n (PPh 3 ) 3 ]. The sulphinylamine cumulene adopts one of three possible bonding geometries (pyramidal, or coplanar through sulphur, or π-coordination through sulphur and nitrogen). The preference for a particular mode in a given complex is discussed in terms of metal electron density, d -orbital occupancy, oxidation state and frontier orbital symmetry. Treatment of the complex [RhCl(PPh 3 ) 2 (OSNSO 2 C 6 H 4 Me-4)] (prepared from tosyliminooxosulphurane and [RhCl(PPh 3 ) 3 ]) with carbon monoxide results in a rearrangement of the π-bond cumulene in the precursor to a pyramidally bound ligand in the CO adduct [RhCl(CO)(PPh 3 ) 2 (OSN-SO 2 C 6 H 4 Me-4)].

The coordination chemistry of iminooxosulphuranes: V. The osmium and iridium series [MLCl(PPh3)2(OSA)] (ML = OsNo, IrCO; A = O, CH2, S, NR; R = o-tolyl, p-tolyl and p-tosyl)☆

Abstract The preparation and characterisation of the two analogous series of compounds [OsCl(NO)(PPh 3 ) 2 (OSA)] (A = O, CH 2 , S, NR; R = C 6 H 4 Me-4, C 6 H 4 Me-2, SO 2 C 6 H 4 Me-4) and [IrCl(CO)(PPh 3 ) 2 (OSA)] (A = O, S, NSO 2 C 6 H 4 Me-4) are described. A comparison of spectroscopic data for the complexes supports the isolobal relationship between the molecules OSA.

The coordination chemistry of iminooxosulphuranes VIII. The coupling of tosyliminooxosulphurane with ethylene, allene, and alkynes coordinated to osmium

The reactions of the zerovalent osmium nitrosyl complexes [OsCl(NO)(PPh3)2(L)] (L ue5fb CH2CH2, CH2CCH2, PhCue5fcCPh, PhCue5fcCH, CH3Cue5fcCCH3 and CF3Cue5fcCCF3) with toluene sulphonyliminooxo-λ4-sulphurane, OSNSO2C6H4Me-4 (OSNSO2R) have been investigated. The ethylene complex reacts either by ethylene substitution to provide [OsCl(NO)(PPh3)2(OSNSO2R)] or by formation of the metallacyclic complex [Os{CH2CH2S(NSO2R)O}Cl(NO)(PPh3)2], which has been crystallographically characterised. The allene complex reacts in a similar manner, also forming a metallacycle [Os{C(ue5fbCH2)CH2S(NSO2R)O}Cl(NO)(PPh3)2]. The reactivity of the alkyne complexes depends upon the nature of the alkyne substituents: the strongly bound hexafluorobut-2-yne complex is unreactive, the but-2-yne complex reacts by alkyne substitution (i.e., formation of [OsCl(NO)(PPh3)2(OSNSO2R)]), and the aryl alkyne complexes react by metallacycle formation to give [Os{CPhue5fbCR′S(NSO2R)O}Cl(NO)(PPh3)2] (R′ ue5fb H, Ph). The metallacyclic derivatives are readily and reversibly protonated (HBF4) at the exocyclic sulphimine substituent.

Synthesis of organometallic hydrotris(pyrazol-1-yl)boratoruthenium(II) complexes

Abstract The reactions of K[HB(pz)3] (pz = pyrazol-1-yl) with the coordinatively unsaturated σ-vinyl complexes [Ru(CRue5fbCHR)Cl(CO)(PPh3)2] (R = H, Me, C6H5) proceed with loss of a chloride and a phosphine ligand to provide the compounds [Ru(CRue5fbCHR)(CO)(PPh3){HB(pz)3}] in high yield. Similar treatment of the complex [Ru(C6H4Me-4)Cl(CO)(PPh3)2] leads to the related σ-aryl derivative [Ru(C6H4Me-4)(CO)(PPh3){HB(pz)3}] whilst the complex [RuClH(CO)(PPh3)3] treated successively with diphenylbutadiyne and K[HB(pz)3] provides the unusual derivative [Ru{C(Cue5fcCPh)ue5fbCHPh}(CO)(PPh3){HB(pz)3}].

The coordination chemistry of iminooxosulphuranes: III. Synthesis of the ruthenium complexes [Ru(OC)(PPh3)2(L)(OSNR)] (L = CO, CNtBu, CNC6H3Me2-2,6; R = C6H4Me-2, C6H4Me-4)☆

Abstract The tris(phosphine) complexes [Ru(CO)(PPh3)3(L)] (L = CO, CNtBu, CNC6H3Me2-2,6) react with iminooxosulphuranes. RNue5fbSue5fbO, (R = C6H4Me-2, C6H4Me-4) by a displacement of one labile phosphine ligand to provide [Ru(CO)(PPh3)2(L)(OSNR)]. Spectroscopic data indicate that the heterocumulenes are bound to ruthenium through both nitrogen and sulphur. Sulphur dioxide coordinates in a similar bidentate mode, through sulphur and oxygen, in the complexes [Ru(CO)(PPh3)2(L)(SO2)] that are obtained upon treatment of the corresponding tris(phosphine) precursors with gaseous sulphur dioxide.

The coordination chemistry of iminooxosulphuranes VII. Coordinative activation of tolyliminooxosulphurane towards electrophiles

Abstract The reactions of the p -tolyliminooxosulphurane complexes [Ru(CO)(L)(PPh 3 ) 2 (OSNR)] (L=CO, CNC 6 H 3 Me-2,6, CN t Bu; R=C 6 H 4 Me-4 ( p -tolyl)) and [OsCl(NO)(PPh 3 ) 2 (OSNR)] with a range of electrophiles have been investigated: [Ru(CO)(CNC 6 H 3 Me 2 -2,6)(PPh 3 ) 2 (OSNR)] reacts with hexafluoroantimonic acid to give the N -protonated salt [Ru(OSNHR)(CO)(CNC 6 H 3 Me 2 -2,6)(PPh 3 ) 2 ]SbF 6 , which in turn reacts with nucleophilic ligands CN t Bu and SCN − to give the η 1 -sulphinamido complexes [Ru(OSNHR)(CO)(CN t Bu)(CNC 6 H 3 Me 2 -2,6)(PPh 3 ) 2 ] + and [Ru(OSNHR)(SCN)(CO)(CNC 6 H 3 Me 2 -2,6)(PPh 3 ) 2 ]. Alkylation of [Ru(CO)(L)(PPh 3 ) 2 (OSNR)] with R′X occurs at oxygen, giving the complexes [Ru(R′OSNR)(CO)(L)(PPh 3 ) 2 ]X (L=CNC 6 H 3 Me 2 -2,6, R′=CH 3 , X=CF 3 SO 3 ; R′=C 2 H 5 , X=SO 3 F; L=CO, R′=CH 3 , X=CF 3 SO 3 ). Silylation of [Ru(CO)(CNC 6 H 3 Me 2 -2,6)(PPh 3 ) 2 (OSNR)] with Me 3 SiOSO 2 CF 3 occurs at oxygen, to give [Ru(Me 3 SiOSNR)(CO)(CNC 6 H 3 Me 2 -2,6)(PPh 3 ) 2 ]O 3 SCF 3 whilst [OsCl(NO)(PPh 3 ) 2 (OSNR)] with BF 3 OEt 2 gives [OsCl(NO)(PPh 3 ) 2 (F 3 BOSNR)]. The adducts formed by reactions of coordinated iminooxosulphuranes with HSbF 6 , Me 3 SiOSO 2 CF 3 and BF 3 OEt 2 reacted with KOH/MeOH, CsF and acetone, respectively to regenerate the zerovalent iminooxosulphurane complexes, but alkylation was found to be irreversible.

Coordinative activation of nitrosoarenes: synthesis and protonation of the osmaoxaziridine [OsCl(NO)(ONC6H5)PPh3)2]

Nitrosobenzene, reacts readily with [OsCl(NO)(PPh3)2(L)] (L = C2H4, PPh3) to replace the labile ligand, L, and form of complex [OsCl(NO)(ONPh)(PPh3)2] in which the nitrosoarene ligand is coordinated through both nitrogen and oxygen. The nitrosobenzene complex reacts reversibly with hydrogen chloride to provide a 11 adduct, formulated as the divalent osmium hydroxylamino complex [OsCl2{N-OH)Ph}(NO)(PPh3)2].

The coordination chemistry of iminooxosulphuranes IX. The insertion reactions of tosyliminooxosulphurane with coordinatively unsaturated ruthenium and osmium aryl complexes

The 16-electron compounds [MRCl(CO)(PPh3)2] (M = Ru, Os; R = C6H4Me-4) react with toluene sulphonyliminooxo-λ4-sulphurane (RSO2NSO, tosyl-NSO) to give the N-(tosyl)toluenesulphinimidato-S complexes [MCl{SR(NSO2R)O}(CO)(PPh3)2] (which are presumably stabilised by weak coordination of a sulphimide group). No reaction is observed between the complexes [MRCl(CO)(PPh3)2] and the less electrophilic iminooxo-λ4-sulphuranes R′NSO (R′ = R, C6H4Me-2, ferrocenyl). In keeping with its coordinative unsaturation, the complex [OsCl{SR(NSO2R)O}(CO)(PPh3)2] reacts with xylyl isonitrile to give [OsCl{SR(NSO2R)O}(CNC6H3Me2-2,6)(CO)(PPh3)2]. No insertion reactions were observed between tosyl-NSO and the 18-electron complexes [Ir(CH3)I(NO)(PPh3)2], [OsRCl(CO)2(PPh3)2], [RuBr(CF3)(CO)2(PPh3)2] and [Ru(C6H5)Cl(CO)(CNC6H3Me2-2,6)(PPh3)2].