TRANSITION-METAL COMPLEXES OF P-RICH PHOS PHANES AND SILYLPHOSPHANES .11. FORMATION, REACTIONS, AND STRUCTURES OF CHROMIUM CARBONYL-COMPLEXES FROM REACTIONS OF LI(THF)(2)[ETA(2)-((T)BU(2)P)(2)P] WITH CR(CO)(5)CENTER-DOT-THF AND CR(CO)(4)CENTER-DOT-NBD

Reactions of Li(THF)(2)[eta(2)-((t)Bu(2)P)(2)P] 1 with Cr(CO)(5) . THF yield Li(THF)(2)Et(2)O[Cr(CO)(4)(eta(1)-Cr(CO)(5)] 2 and the compound s [Cr(CO)(4)(eta(2)-((t)Bu(2)P)(2)PH)] 3, [Cr(C))(5)(eta(1)-((t)Bu(2)) P2PH)] 4, ((t)Bu(2)P)(2)PH 5 and Bu(2)PH . Cr(CO)(4) 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 12-crown-4)(2)[Cr(CO)(4)-(eta(2 )-((t)Bu(2)P)(2)P)] 7 (yellow crystals). 7 reacts with CH3COOH to 3 - which regenerates 7 with LiBu - with Cr(CO)(5)THF to compound 2, with NBD . Cr(CO)(4) in THF to 2 and 3 (ratio 1:1). With EtBr, 7 forms [Cr( CO)(4)(eta(2)-((t)Bu(2)P)(2)PEt)] 8, and [Cr(CO)(4)(eta(2)-((t)Bu(2)P) (2)PBr)] 9 with BrCH2-CH2Br. The compounds were characterized by means of H-1, C-13, P-31, Li-7 NMR spectroscopy, IR spectroscopy, elementar y analysis, mass spectra, and 2, 3 and 4 additionally by means of X-ra y diffraction analysis. 2 crystallizes in the space group P (1) over b ar with 2 formula units in the elementary cell; a = 10.137(9), b = 15. 295(12), c = 15.897(14) Angstrom, alpha = 101.82(7), beta = 91.65(7), gamma = 98.99(7)degrees; 3 crystallizes in the space group P2(1)/n wit h 4 molecules in the elementary unit; a = 11.914(6), b = 15.217(10), c = 14.534(10) Angstrom; alpha = 90, beta = 10.3.56(5), gamma = 90 degr ees, 4: space group P (1) over bar with 2 molecules in the elementary unit; a = 8.844(4), b = 12.291(6), c = 14.411(7) Angstrom, alpha = 66. 55(2), beta = 89.27(2), gamma = 71.44(2)degrees.