Chiral hexarhodium clusters containing heterobidentate phosphine ligands, a structural and reactivity study

Some intrinsically chiral [Rh6(CO)14(µ,2-PX)] clusters have been synthesized, beginning with reactions of [Rh6(CO)16–x(NCMe)x](x= 1, 2) with PX, where PX represents the bidentate bridging ligands diphenyl(benzothienyl)phosphine (1), diphenyl(2-thienyl)phosphine (2), di(2-thienyl)phenylphosphine (3), tris(2-thienyl)phosphine (4), diphenyl(2-pyridyl)phosphine (5) and diphenylvinylphosphine (6). The ligand tris(2-furyl)phosphine (7) shows no bridging capability. When x= 1 the initial products are the clusters [Rh6(CO)15(1-PX)] which undergo spontaneous CO loss to form [Rh6(CO)14(µ,2-PX)]. The structures of the [Rh6(CO)15(1-PX)] clusters have been elucidated by IR, NMR spectroscopy and FAB-MS spectrometry, and have been found to involve phosphorus atom coordination to a rhodium atom. In addition, the solid state structures of the [Rh6(CO)14(µ,2-Ph2P(2-benzothienyl))](8), [Rh6(CO)14(µ,2-Ph2P(2-thienyl))](9), [Rh6(CO)14(µ,2-PhP(2-thienyl)2)](10) and [Rh6(CO)14(µ,2-Ph2P(pyridyl))](12) clusters have been determined by X-ray crystallography. The various types of chirality exhibited by these clusters are discussed. A simple model is proposed to account for the ratios of stereochemical isomers found in the Rh6(CO)14(µ,2-PhP(2-thienyl)2 cluster. The kinetics of formation of the bridged clusters from the monosubstituted [Rh6(CO)15(1-PX)] clusters have been studied.

Koshevoy, I O (författare)
Poe, A J (författare)
Farrar, D H (författare)
Nordlander, EbbeLund University,Lunds universitet,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH(Swepub:lu)ook1-eno (författare)
Pakkanen, T A (författare)
Haukka, M (författare)
Kemiska institutionenInstitutioner vid LTH (creator_code:org_t)

Ingår i:Dalton Transactions: Royal Society of Chemistry (RSC):12, s. 2457-24671477-9234
Ingår i:Dalton Trans.: Royal Society of Chemistry (RSC):12, s. 2457-24671477-9226

Av författaren/redakt...: Tunik, S P; Koshevoy, I O; Poe, A J; Farrar, D H; Nordlander, Ebbe; Pakkanen, T A; visa fler...; Haukka, M; visa färre...

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