Reaction between [Re3H3(CO)12] and the diphosphine ligands Ph2P-CH2PPh2 and (EtO) 2POP(OEt)2: X-ray crystal structures of [Re 2H2-(CO)6(Ph2PCH2PPh 2)]...

David W. Prest, Martin J. Mays, Paul R. Raithby, A. Guy Orpen

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Abstract

full title:Reaction between [Re3H3(CO)12] and the diphosphine ligands Ph2P-CH2PPh2 and (EtO) 2POP(OEt)2: X-ray crystal structures of [Re 2H2-(CO)6(Ph2PCH2PPh 2)] and [Re3H3(CO)8{(EtO) 2POP(OEt)2}2] The reactions of [Re3H3(CO)12] with the diphosphine ligands Ph2PCH2PPh2 (dppm), (EtO)2POP(OEt)2 (tedip), and Ph2PCH 2CH2PPh2 (dppe) have been studied. From the reaction with dppm, the known complex [Re2- (CO)8(dppm)] (1) has been isolated together with the three new complexes [Re 2H2(CO)6(dppm)] (2), [Re3H 3-(CO)10(dppm)] (3), and [Re3H 3(CO)8(dppm)2] (4). The reaction of [Re 3H3(CO)12] with tedip proceeds similarly to that with dppm, forming products (5), (6), and (7) analogous to (2), (3), and (4), and a second isomer of (6), [Re3H3(CO) 10(tedip)] (8), in which a tedip ligand chelates a single rhenium atom in an axial-equatorial configuration. Protonation of (7) gives the cation [Re3H4(CO)8(tedip)2]+ (10). Complexes (2) and (7) have been characterised by X-ray structure analysis by conventional heavy-atom methods using room-temperature diffractometer data. Complex (2) crystallises in space group Pbca with Z = 8, a = 19.220(5), b = 29.820(9), and c = 10.655(4) Å, and (7) in space group P21/c with Z = 4, a = 18.053(6), b = 16.211(5), c = 14.800(3) Å, and β = 102.41(2). Final residuals were R = 0.033 and 0.0696 for 2 247 and 3 398 unique observed intensity data respectively. In (2) the dppm ligand and two hydride ligands bridge the (formal) Re-Re double bond. In (7) the Re3(μ-H) 3 core of [Re3H3(CO)1 2] is preserved with four axial sites occupied by the two tedip ligands which bridge two edges of the Re3 triangle. The reaction between [Re 3H3(CO)12] and dppe gives [ReH(CO) 3(dppe)] as the major product; a minor product isolated in low yield is formulated as [Re2H(CO)7(Ph2PCH 2CH2PPhC6H4)] (9).

Original languageEnglish
Pages (from-to)737-745
Number of pages9
JournalJournal of the Chemical Society, Dalton Transactions
Issue number4
DOIs
Publication statusPublished - 31 Dec 1982

ASJC Scopus subject areas

  • General Chemistry

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