Reaction of Bulky Monosubstituted Phosphorus(III) Halides with Disodium Pentacarbonylchromate. Steric and Electronic Factors in the Synthesis of Cr(CO)5 Complexes of Diphosphenes, Phosphinidenes, Phosphanes, Diphosphanes, and Cyclopolyphosphanes

Article abstract of DOI:10.1021/ja00253a021

Reaction of Na2Cr(CO)5 with bulky monosubstituted phosphorus(III) halide, RPCl2, where R=2,4,6-Me3C6H2 (Mes), CH2SiMe3, CH(SiMe3)2, N(SiMe3)2, or -OC6H2-2,6-t-Bu2-4-Me, leads to at least nine different types of product which may involve diphosphene, phosphinidene, phosphane, diphosphane, and cyclopolyphosphane ligands.The product obtained depend markedly on the size and electronic properties of the substituent on phosphorus.The synthesis and properties of 12 compounds of which 10 have been structurally characterized by X-ray crystallography are described in this paper.IR and 31P NMR data are also reported.The compounds are 2 (1a), <(Cr(CO)5)2(P(H)Mes)2> (2), (3), <(Cr(CO)5)2(cyclo-(PCH2SiMe3)4)> (5), (6), (7), (8), <(Cr(CO)5)2PN(SiMe3)2> (9), (10), (11), and <(Cr(CO)5)2(POC6H2-2,6-t-Bu2-6-Me)> (12).Details of the structures of complexes 1a, 2, 3, 5, and 6 in addition to 11 and 12 are described and discussed in conjunction with those of 7, 9, and 10 which have been reported in preliminary publications.Crystal data α (λ=0.71069 Angstroem)> at 130 K are as follows: 1a, C28H22Cr2P2O10, a=11.170(6) Angstroem, b=16.159(8) Angstroem, c=9.260(5) Angstroem, β=113.91(4) deg, Z=2, monoclinic, space group P2₁/c, R=0.0745; 2, C28H22Cr2P2O10.C6H14, a=9.008(4) Angstroem, b=9.418(4) Angstroem, c=11.625(3) Angstroem, α=96.77(3) deg, β=112.21(3) deg, γ=94.69(4) deg, Z=1, triclinic, space group P1, R=0.052; 3, C32H33CrP3O5, a=10.507(6) Angstroem, b=11.437(7) Angstroem, c=14.707(9) Angstroem, α=110.95(4) deg, β=9.49(5) deg, γ=104.48(4) deg, Z=2, triclinic, space group P2₁/c, R=0.045; 5, C26H44Cr2P4O10Si4, a=10.322(4) Angstroem, b=19.180(4) Agstroem, c=11.198(4) Angstroem, β=109.79(2) deg, Z=2, monoclinic, space group P2₁/c, R=0.050; 6, C18H22Cr2P2O10Si2, a=6.989(3) Angstroem, b=9.226(4) Angstroem, c=10.975(5) Angstroem, α=106.08(3) deg, β=93.36(3) deg, γ=94.58(3) deg, Z=1, triclinic, space group P1, R=0.064; 11, C20H23CrPO6Cl2, a=13.068(2) Angstroem, b=11.426(3) Angstroem, c=20.15.852(4) Angstroem, β=93.81(2) deg, Z=4, monoclinic, space group P2₁/a, R=0.031; 12, C25H23Cr2PO11 (at 293 K), a=9.224(1) Angstroem, b=16.549(2) Angstroem, c=20.240(2) Angstroem, α=73.74(1) deg, β=80.44(1) deg, γ=87.50(1) deg, Z=4, (2 dimers), triclinic, space group P1, R=0.056.