Reactions of Transition Metal Nitrogen sigma-Bonds. 5. Carbonation of Tetrakisdiethylamido Chromium (IV) to Yield Binuclear Chromium (III) and -(II) Carbamato Complexes.
Abstract
From the reaction between Cr(NEt)4 and CO2 (4 equiv) two crystalline compounds have been isolated and structurally characterized: I, Cr2(O2CNEt2)4(Mu-NEt2)2 and II, Cr2(O2CNEt2)42HNEt2. Compound I is the major product when CO2 is allowed to react slowly with Cr(NEt2)4; compound II predominates when CO2(4 equiv) is added rapidly. These results are compared with previous studies of CO2 insertion reactions involving early transition metal dialkylamides and with the known reactions of Cr(NEt2)4. A reaction pathway leading from Cr(NEt2)4 to I and II is proposed to involve beta-hydrogen elimination from a (CR(IV) -NEt2) moiety followed by reductive elimination of ET2NH and the generation of Cr(II). I crystallizes in space group Pbcn with a = 19.122(8), b = 11.024(2), c = 18.114(6)A, V = 3818(3)A(3), and Z = 4. II crystalizes in the space group Pl with a = 10.936(2), b = 11.170(2), c = 8.871(2)A, alpha = 99.46(1), beta = 98.56(1), gamma = 108.58(1), V = 989.4(6)A(3), and Z = 2.
Document Details
- Document Type
- Technical Report
- Publication Date
- Apr 20, 1978
- Accession Number
- ADA053491
Entities
People
- D. C. Rideout
- F. A. Cotton
- M. H. Chisholm
- M. W. Extine
Organizations
- Princeton University