Synthesis and Reactions of 2-C2H4)> (dppm=Ph2PCH2PPh2): Crystal Structure of the 1:2 Chlorobenzene Solvate

DOI: 10.1039/DT9870001763

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1763 - 1768 (1987)

Update date:2022-07-29

Topics:

Authors:

Carr, Stuart W.

Shaw, Bernard L.

Thornton-Pett, Mark

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Article abstract of DOI:10.1039/DT9870001763

Treatment of with Ph2PCH2PPh2 (dppm) gives mer,cis- (1).The uncomplexed phosphorous of (1) is readily quaternized by to give mer,cis-BF4 (2).Treatment of complex (1) with gives <(OC2)Re(μ-dppm)2(μ-Cl)2Rh(ν²-C2H4)> (3).The ethylene ligand in (3) is readily displaced by allene to give <(OC)2Re(μ-dppm)2(μ-Cl)2Rh(ν²-C3H4)> (4).When complex (3) is treated with dihydrogen <(OC)2Re(μ-dppm)2(μ-Cl)(μ-H)(RhH(Cl)> (5) is formed; with CO (6) is initially formed but this reacts further to give <(OC)3Re(μ-dppm)2(μ-Cl)Rh(CO)>Cl (7a).The complexes (6) and (7a) were more readily prepared by treating (1) with .The chloride salt (7a) was converted into the corresponding PF6 (7b) and BPh4 (7c) salts.We also report the corresponding iridium salt <(OC)3Re(μ-dppm)2(μ-Cl)Ir(CO)>PF6 (8).N.m.r. and i.r. data are given.Crystals of (3) are monoclinic, space group P2₁/n (=P2₁/c, no. 14) with a = 1 027.5(8), b = 2 996.5(9), c = 2 142.2(5) pm and β = 92.50(2) deg; final R and R' values 0.0485 and 0.0518, respectively for 6 816 unique reflections with Ι>2.0?(Ι).The crystal structure shows an ν²-ethylene, terminally bound to the rhodium atom, with an unusually long carbon-carbon distance <150(2) pm>.