ISSN:
0044-2313
Keywords:
Formation of Li(THF)2Et2O[Cr(CO)4{η2-(tBu2P)2P}ηt-Cr(CO)5] 2, [Cr(CO)4{η2-(tBu2P)2PH}] 3, [Cr(CO)5{η1-(tBu2P)2PH}] 4 from Cr(CO)5THF and Li(THF)2[η2-(tBu2P)2P] 1, as well as of Li(12-crown-4)2[Cr(CO)4{η2-(tBu2P)2P}] 7 from 1 and NBD · Cr(CO)4. 7 forms with Cr(CO)5THF 2, with CH3COOH 3, with EtBr [Cr(CO)4{η2-(tBu2P)2PEt}] 8, with BrCH2—CH2Br [Cr(CO)4{η2-(tBu2P)2PBr}] 9. Crystal structures of 2, 3 and 4
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
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 · NBDReactions 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)°.
Notes:
Umsetzungen von Li(THF)2[η2-(tBu2P)2P] 1 mit Cr(CO)5 · THF führen zum Li(THF)2Et2O[Cr(CO)4{η2-(tBu2P)2P}η1-Cr(CO)5] 2 sowie zu [Cr(CO)4{η2-(tBu2P)2PH}] 3, [Cr(CO)5{η1-(tBu2P)2PH}] 4, (tBu2P)2PH 5 und tBu2PH · Cr(CO)5 6, wobei die Bildung von 3, 4, 5 und 6 auf Nebenprodukte aus der Herstellung von 1 zurückgeht. 2 reagiert mit CH3COOH unter Bildung von 3. 1 bildet mit NBD · Cr(CO)4 in THF nach Zugabe von 12-Krone-4 das Li(12-Krone-4)2[Cr(CO)4{η2-(tBu2P)2P}] 7 (gelbe Kristalle). 7 reagiert mit CH3COOH zu 3 - aus dem sich mit LiBu Verbindung 7 zurückbildet -, mit Cr(CO)5THF zu Verbindung 2, mit NBD · Cr(CO)4 in THF zu 2 und 3 (Verhältnis 1 : 1). 7 bildet mit EtBr das [Cr(CO)4{η2-(tBu2P)2PEt}] 8, mit BrCH2—CH2Br das [Cr(CO)4{η2-(tBu2P)2PBr}] 9. Die Verbindungen wurden über ihre 1H-, 13C-, 31P-, 7Li-NMR-Spektren, IR-Spektren, Elementaranalysen und Massenspektren charakterisiert sowie 2, 3 und 4 durch Röntgenstrukturanalysen.2 kristallisiert in der Raumgruppe P1 mit 2 Formeleinheiten pro Elementarzelle; 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 in Raumgruppe P21/n mit 4 Molekülen in der Elementarzelle; a = 11,914(6), b = 15,217(10), c = 14,534(10) Å; α = 90, β = 103,56(5), γ = 90°. 4 in Raumgruppe P1 mit 2 Molekülen pro Elementarzelle; 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)°.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19966220107
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