| Abstract: | Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. XI. Formation, Reactions, and Structures of Chromium Carbonyl Complexes from Reactions of Li(THF)2[η2-(tBu2P)2P] with Cr(CO)5 · THF and Cr(CO)4 · NBD Reactions of Li(THF)2[η2-(tBu2P)2P] 1 with Cr(CO)5 · THF yield Li(THF)2Et2O[Cr(CO)4{η2-(tBu2P)2P}η1-Cr(CO)5] 2 and the compounds [Cr(CO)4{η2-(tBu2P)2PH}] 3 , [Cr(CO)5{η1-(tBu2P)2PH}] 4 , (tBu2P)2PH 5 and tBu2PH · Cr(CO)5 6 . The formation of 3, 4, 5 and 6 is due to byproducts coming from the synthesis of 1. 2 reacts with CH3COOH under formation of 3 . After addition of 12-crown-4 1 with NBD · Cr(CO)4 in THF forms Li(12-crown-4)2[Cr(CO)4-{η2-(tBu2P)2P}] 7 (yellow crystals). 7 reacts with CH3COOH to 3 – which regenerates 7 with LiBu – with Cr(CO)5THF to compound 2 , with NBD · Cr(CO)4 in THF to 2 and 3 (ratio 1 : 1). With EtBr, 7 forms [Cr(CO)4{η2-(tBu2P)2PEt}] 8 , and [Cr(CO)4{η2-(tBu2P)2PBr}] 9 with BrCH2? CH2Br. The compounds were characterized by means of 1H, 13C, 31P, 7Li NMR spectroscopy, IR spectroscopy, elementary analysis, mass spectra, and 2, 3 and 4 additionally by means of X-ray diffraction analysis. 2 crystallizes in the space group P1 with 2 formula units in the elementary cell; a = 10.137(9), b = 15.295(12), c = 15.897(14) Å; α = 101.82(7), β = 91.65(7), γ = 98.99(7)°; 3 crystallizes in the space group P2t/n with 4 molecules in the elementary unit; a = 11.914(6), b = 15.217(10), c = 14.534(10) Å; α = 90, β = 103.56(5), γ = 90°. 4 : space group P1 with 2 molecules in the elementary unit; a = 8.844(4), b = 12.291(6), c = 14.411(7) Å, α = 66.55(2), β = 89.27(2), γ = 71.44(2)°. |
