Terence V. Ashworth

Cobalt chloride: An inexpensive catalyst for the substitution of CO by isonitriles on M(CO)6 (M = Cr, Mo, W)

Abstract CoCl 2 · 2 H 2 O has been found to catalyse the substitution of CO on Group VI metal carbonyls by isonitriles to yield M(CO) 6− n (RNC) n [M = Cr, Mo, W, n = 1—3, RNC = t-BuNC; M = Cr, Mo, W, n = 1, RNC = MeNC, XNC (2,6-dimethylphenylisocyanide); M = Mo, n = 2, R = MeNC, XNC; fac -Mo(CO) 3 (MeNC) 3 and cis -Mo(CO) 2 (t-BuNC) 4 ]. The reactions occur by stepwise replacement of the CO groups and mixed isonitrile derivatives can readily be prepared e.g. Mo(CO) 4 (MeNC)(t-BuNC). All the reported reactions are facile and product yields typically 80–95%.

The transition metal-catalysed reaction between Fe(CO)5 and group V donor ligands. A facile, high yield synthesis of Fe(CO)4PPh3

Abstract The reaction of Fe(CO) 5 and L (L = Group V donor ligand), in the presence of CoCl 2 · 2 H 2 O or CoI 2 · 4 H 2 O as catalyst, results in the synthesis of Fe(CO) 4 L in good yield. Unusual reactivity patterns for the substitution of CO on Fe(CO) 5 by L have been found; for CoI 2 as catalyst the reaction rate increases in the order PPh 3 ∼ AsPh 3 ∼ P(OPh) 3 > SbPh 3 > PPh 2 Me > PPhMe 2 > P(C 6 H 11 ) 3 > P(OEt) 3 > P(n-Bu) 3 > P(OMe) 3 . These results are interpreted in terms of the variation of the catalyst through interaction of CoX 2 with L.

Formation of cationic and neutral carbamato and related ruthenium(II) complexes from reaction of CO2, COS and CS2 with ruthenium hydrides in alcohol solution containing HNMe2. The crystal structure of [Ru(O2CNMe2)(PMe2Ph)4]PF6

The salts [Ru(XYCR)(PMe2Ph)4]PF6 (XY = OS, R = OEt; XY = S2, R = H), [Ru(XYCNMe2)(PMe2Ph)4]PF6 (XY = O2, OS, S2) and the neutral product [RuH(O2CNMe2)(PPh3)3] are formed by interaction of CO2, COS or CS2 with [RuH(PMe2Ph)5]PF6 or [RuH2(PPh3)4] in ethanol or ethanol/dimethylamine mixtures; the crystal structure of [Ru(O2CNMe2)(PMe2Ph)4]PF6 has been determined.

The catalytic substitution of metal carbonyls and substituted metal carbonyls by isonitriles in the presence of rhodium(I) and polymer-supported rhodium(I) complexes

Abstract Metal carbonyls and substituted metal carbonyls, under relatively mild reaction conditions, in the presence of isonitriles, undergo catalytic CO substitution by rhodium(I) and polymer-supported rhodium(I) complexes. The reaction provides a facile route to the synthesis of transition metal isonitrile metal isonitrile complexes.

The Preparation and Reactions of Cationic Ruthenium(II) Complexes Containing 1,5-Cyclooctadiene and Acetonitrile

Abstract The polymer [(C 8 H 12 )RuCl 2 ] x , (C 8 H 12  1,5-cyclooctadiene, x > 2), dissolves in refluxing acetonitrile to form [(C 8 H 12 )RuCl(CH 3 CN) 3 ] + and, on treatment with AgPF 6 , [(C 8 H 12 )Ru(CH 3 CN) 4 ] 2+ ; some reactions of these cations are described.

Hydrogen transfer processes in the formation of cationic η5 -dienyl complexes of ruthenium(II): X-ray structure of [Ru(1-5-η-cyclooctadienyl)(PMe2Ph)3][PF6]

Abstract The cations [Ru(1—3:5—6-η-C 8 H 11 )(η 6 -1,3,5-cyclooctatriene)] + ( 2 ) and [RuH(COD)L 3 ] + ( 5 ) (COD = cycloocta-1,5-diene, L = PMe 2 Ph, AsMePh 2 ) are convenient precursors to a range of η 5 -dienyl complexes of ruthenium(II); evidence for hydrogen transfer processes is presented.

Formation of the η5-bicyclo[5.1.0]octadienyl ligand by reaction of cyclooctatetraene with a ruthenium(II) hydride complex: Molecular structure of [Ru(2–6-η-bicyclo[5.1.0]octadienyl)(PMe2Ph)3][PF6]

Abstract [Ru(2–6-η-bicyclo[5.1.0]octadienyl)(PMe 2 Ph) 3 ][PF 6 ], formed from the reaction of cyclooctatetraene with [RuH(COD)(PMe 2 Ph) 3 ][PF 6 ] (COD = cycloocta-1,5-diene), has been characterised spectroscopically from 1 J (CH) coupling constants and an X-ray structural analysis; the bicyclic ligand contains an elongated bridging CC bond (1.63 A).

X-ray structure of fac-[RuH(1,5-cod)(NH2NMe2)3][PF6]: Stabilization of coordinated substituted hydrazines by hydrogen bonding

Abstract The structure of [RuH(cod)(NH2NMe2)3][PF6] has been solved by X-ray diffraction methods and shows the cation to contain a facial arrangement of N,N-dimethylhydrazine ligands, coordinated via the NH2 nitrogen atoms, and held together by hydrogen bonds.

Cationic hydrido-olefin complexes of ruthenium (II). The crystal structure of hydrido(1,3-butadiene)tris-(dimethylphenylphosphine)ruthenium(II) hexafluoro-phosphate

Abstract A route to the stable hydrido-diene salts [(diene)RuHL 3 ] PF 6 , (diene = cycloocta-l,5-diene, hexa-l,3-diene and buta-1,3-diene, L = PMe 2 Ph; diene = cycloocta-l,5-diene, L = P(OMe) 3 , P(OCH 2 ) 3 CMe P(OMe)Ph 2 and PMePh 2 ) has been found and the structure of [RuH(C 4 H 6 )(PMe 2 Ph) 3 ] PF 6 has been determined by X-ray diffraction.