Rhodium complexes with secondary phosphine and phosphinite ligands and the crystal structures of [(PPh2OH)2(PPh2O)Rh(μ-Cl)3Rh(PPh2OH)(PPh2O)2] and [(PPh2OH)(PPh2O)Cl(NCMe)Rh(μ-Cl)2Rh(PPh2OH)(PPh2O)Cl(NCMe)] · 2thf

Patel, Bhavesh, Pope, Simon J. A. ORCID: https://orcid.org/0000-0001-9110-9711 and Reid, Gillian 1998. Rhodium complexes with secondary phosphine and phosphinite ligands and the crystal structures of [(PPh2OH)2(PPh2O)Rh(μ-Cl)3Rh(PPh2OH)(PPh2O)2] and [(PPh2OH)(PPh2O)Cl(NCMe)Rh(μ-Cl)2Rh(PPh2OH)(PPh2O)Cl(NCMe)] · 2thf. Polyhedron 17 (13-14) , pp. 2345-2351. 10.1016/S0277-5387(97)00460-9

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Abstract

RhCl3·3H2O reacts with ca six molar equivalents of PPh2H or PCy2 in EtOH solution under a N2 atmosphere and in the presence of excess NH4PF6 to yield [RhCl2(PPh2H)4]Pf6 or [RhCl2(PCy2H)4]PF6 respectivley as yellow solids. 31P{1H} NMR spectroscopy shows the presence of the trans isomer only in chloro-carbon solutions, with JRhP ca 80 Hz. Upon standing a solution of trans-[RhCl2(PPh2H)4]PF6 in a MeCH/thf mixture results in the production of yellow crystals of [(PPh2OH)(PPh2OCl(NCMeRh(μ-Cl)2Rh(rmPPh2OH)(PPH2O)Cl(NCMe)]·2thf, the structure of which shows an edge-bridge bioctahedral arrangement with View the MathML source. The NCMe ligands to the terminal Cl ligands, while the PPh2O and PPh2O− ligands are trans to the bridging Cl ligands. The crystal structure of the triply-bridged dimer [(PPh2OH)2(PPh2O)Rh(μ-Cl)3Rh(PPh2OH)(PPh2O)2] has aslo been determined, showing a face-sharing bioc-tahedral arrangement, with View the MathML source. Both dinuclear species show significant POH…OP hydrogen-bonding interactions.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Subjects:	Q Science > QD Chemistry
Publisher:	Elsevier
ISSN:	0277-5387
Last Modified:	21 Oct 2022 10:54
URI:	https://orca.cardiff.ac.uk/id/eprint/41657

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