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Bimetallic Systems. Part 16. Formation of Group 6 Meta(0)-Platinum(II) Hydride Complexes, by Ring Opening of fac- or mer- (M = Cr, Mo, or W; dppm = Ph2PCH2PPh2). Reactions of

DOI: 10.1039/DT9870000221

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 221 - 226 (1987)

Update date:2022-08-02

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Authors:

Blagg, AdrianBlagg, Adrian

Shaw, Bernard L.Shaw, Bernard L.

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Article abstract of DOI:10.1039/DT9870000221

The new complexes fac- and mer- (dppm = Ph2PCH2PPh2) are described.Treatment of fac- or mer- (M = Cr, Mo, or W) with trans- gave the heterobimetallic complexes <(CO)3M(μ-dppm)2PtH(Cl)> in good yields.Similarly fac- or mer- reacted with trans-CPh)(PPh3)2> to give <(CO)3Mo(μ-dppm)2PhH(C<*>CPh)>, but the corresponding chromium- or tungsten-platinum complexes could not be prepared.Phosphorus-31 and 1H n.m.r., and i.r. spectroscopic data are given and discussed. 1H-<31P> N.m.r. studies at different temperatures showed the complexes of type <(CO)3M(μ-dppm)2PtH(Y)> (M = Cr, Mo, or W, Y = Cl; M = Mo, Y = C<*>CPh) to be fluxional, corresponding to inversion of the M(μ-dppm)2Pt ring and exchange of positions of the H and Y ligands: a mechanism for this inversion is suggested.The chloride ligand of <(CO)3Mo(μ-dppm)2PtH(Cl)> was found to be readily substituted by nucleophiles Y (Y = Br, CN, N3, H, or CO) to give new heterobimetallic species.Treatment of <(CO)3Mo(μ-dppm)2PtH(Cl)> with NaBH4 gave a heterobimetallic dihydride with a bridging and a terminal hydride. 1H-<31P> N.m.r. studies showed this dihydride to undergo bridging-to-terminal hydride exchange at +21 deg C in solution.

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Product name:fac-{W(CO)3(η1-Ph2PCH2PPh2)(η2-Ph2PCH2PPh2)

Cas No:93453-38-4

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