Dimeric (tris(tert-butyl)silyl)phosphanyl (tris(tert-butyl)silyl)phosphanediyl gallane: a molecule with a Ga-P-Ga heteroallyl system |
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Authors: | Weinrich Sabine Piotrowski Holger Vogt Martin Schulz Axel Westerhausen Matthias |
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Institution: | Department Chemie und Biochemie, Ludwig-Maximilians-Universit?t München, Butenandtstrasse 9, D-81377 Munich, Germany. |
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Abstract: | The metathesis reaction of potassium (tris(tert-butyl)silyl)phosphanide with GaCl(3) in a molar ratio of 1:1 leads to the formation of Cl(2)GaP(H)Si(t)Bu(3)](2) (1) as a mixture of cis and trans isomers with very large (1)J(P,H) and (2)J(P,P) coupling constants. The molecular structure of 1 shows a Ga(2)P(2) cycle with nearly planar coordinated phosphorus atoms under neglection of the hydrogen atoms and Ga-P distances of 239 pm. The reaction of GaCl(3) with 3 equiv of potassium (tris(tert-butyl)silyl)phosphanide as well as the reaction of 1 with 2 equiv of KP(H)Si(t)Bu(3) yields (t)Bu(3)SiP(H)Ga(mu-PSi(t)Bu(3))](2) (2). The central moiety comprises a four-membered Ga(2)P(2) cycle with one planar P atom and extremely short Ga-P bonds of approximately 226 pm, the other being in a pyramidal environment with an angle sum of 298.4 degrees. The structure of 2 can be described as a GaPGa heteroallyl system which is bonded to a phosphanidyl substituent. This idea and its dependency on the steric demand of the trialkylsilyl groups are investigated by DFT calculations on different isomers of 2. |
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