Pentafluorophenylphosphine complexes of rhodium(I): extended X-ray absorption fine structure studies of [{Rh[PPhx(C6F5)3 –x]2(µ-CI)}n](x= 0–2) and [{Rh[(C6F5)2PCH2CH2P(C6F5)2](µ-CI)}2]. Crystal structures of [RhCl(PPh3){(C6F5)2PCH2CH2P(C6F5)2}]·C4H8O and (C6F5)2PCH2CH2P(C6F5)2
- 1 January 1995
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 24,p. 4029-4037
- https://doi.org/10.1039/dt9950004029
Abstract
The NMR spectroscopic properties of the rhodium pentafluorophenylphosphine complexes [{Rh[PPhx(C6F5)3 –x]2(µ-Cl)}n](x= 0 1, 1 2 or 2 3) and trans-[Rh{PPhx(C6F5)3 –x}2Cl(CO)](x= 0 5, 1 6 or 2 7) have been investigated. The new complexes [{Rh[(C6F5)2PCH2CH2P(C6F5)2](µ-Cl)}2]4 and cis-[Rh{(C6F5)2PCH2CH2P(C6F5)2}Cl(CO)]8 have been prepared. A rhodium K-edge extended X-ray absorption fine structure (EXAFS) study of complexes 1–4 has been performed, and confirms that complexes 2, 3 and 4 are dimers with each Rh ⋯ Rh′ distance bridged by two chlorides [d(Rh–P) 2.16–2.21, d(Rh–Cl) 2.38–2.39, d(Rh ⋯ Rh′) 3.50–3.58 Å], whereas complex 1 is a polymer with each Rh ⋯ Rh′ distance bridged by one chloride [d(Rh–P) 2.18, d(Rh–Cl) 2.36, d(Rh ⋯ Rh′) 4.30 Å]. The reaction between [{Rh[(C6F5)2PCH2CH2P(C6F5)2](µ-Cl)}2] and PPh3 yields the four-co-ordinate mononuclear rhodium(I) complex [RhCl(PPh3){(C6F5)2PCH2CH2P(C6F5)2}]9. The crystal structures of 9 and of (C6F5)2PCH2CH2P(C6F5)2 have been determined by X-ray crystallography. Complex 9 crystallizes in the monoclinic space group P21/c with a= 12.707(2), b= 17.066(2), c= 22.003(3)Å, β= 101.41(1)°, z= 4. Refinement gave final R1 and wR2 values of 0.0429 and 0.0715 for 5193 observed reflections. The geometry about the rhodium atom is distorted-square planar and there is a short distance between an ortho-hydrogen atom of the triphenylphosphine ligand and the rhodium atom (2.699 Å) indicative of an agostic interaction. The phosphine (C6F5)2PCH2CH2P(C6F5)2 crystallizes in the triclinic space group P with a= 5.833(1), b= 10.011(2), c= 11.514(4)Å, α= 75.25(2), β= 88.69(2), γ= 84.28(2)°, z= 1. Refinement gave final R1 and wR2 values of 0.0482 and 0.0987 respectively for 1339 observed reflections.Keywords
This publication has 32 references indexed in Scilit:
- Tris(2,6-difluorophenyl)phosphite complexes of platinum group metals: Structure of trans-PtCl2(PEt3){P(O-2,6-C6H3F2)3}Polyhedron, 1995
- Synthesis and structure of η5-pentamethylcyclopentadienyldichloro-iridiumtris(2,6-difuluorophenyl)phosphitePolyhedron, 1993
- Nickel-(II), -(III) and -(IV) complexes of 1,2-bis(dimethylarsino)tetrafluorobenzene and X-ray crystallographic and extended X-ray absorption fine structure studies of nickel-(III) and -(IV) bromo complexesJ. Chem. Soc., Dalton Trans., 1991
- Remarkable effects of a pentafluorophenyl group on the stereoselective reactions of a chiral iron acyl complexJournal of the American Chemical Society, 1988
- Coordination chemistry of higher oxidation states. 19. Synthesis and properties of diphosphine and diarsine complexes of iron(IV), and iron K-edge EXAFS data on [Fe(o-C6H4(PMe2)2)2Cl2]n+[BF4]n (n = 0-2)Inorganic Chemistry, 1986
- Phosphorus-31 nuclear magnetic resonance studies of polymer-anchored rhodium(I) complexesJournal of the American Chemical Society, 1980
- Crystal and molecular structure of bis(triphenylphosphine)rhodium(I) chloride dimer-ethyl acetateInorganic Chemistry, 1978
- High-resolution fluorine-19 nuclear magnetic resonance spectroscopy. Studies of some Group V fluorophenyl derivativesJ. Chem. Soc. A, 1969
- Pentafluorophenyl derivatives of phosphorus, arsenic, and antimony and their complexes with rhodium, palladium, and platinumJ. Chem. Soc. A, 1968
- Preparations and reactions of tris(pentafluorophenyl)phosphine, phenylbis(pentafluorophenyl)phosphine, and diphenylpentafluorophenylphosphine complexes of rhodiumJ. Chem. Soc. A, 1968