B. Rademacher et al., HETEROLEPTIC DIORGANYLZINC COMPOUNDS WITH A BIS(TRIMETHYLSILYL)PHOSPHIDO SUBSTITUENT, Zeitschrift fur anorganische und allgemeine Chemie, 621(2), 1995, pp. 287-300
Citations number
34
Categorie Soggetti
Chemistry Inorganic & Nuclear
Journal title
Zeitschrift fur anorganische und allgemeine Chemie
Dialkylzinc ZnR2 (Me, Et, iso-Pr, nBu, tBu, CH2SiMe3) reacts with one
equivalent of bis(trimethylsilyl)-phosphine in carbohydrates to the he
teroleptic compounds RZnP(SiMe3)2; dependent from the steric demand of
the alkyl group R the derivatives are dimeric or trimeric in solution
as well as in the solid state. Monomeric thylsilyl)phosphido-tris(tri
methylsilyl)methylzinc yields from the reaction of lithium tris(trimet
hylsilyl)methanide and lithium bis(trimethylsilyl)phosphide with zinc(
II) chloride. Bis(trimethylsilyl)phosphido-methylzinc crystallizes in
the orthorhombic space group P2(1)2(1)2(1) with {a = 1007.6(1); b = 18
72.3(3); c = 2231.0(4) pm; Z = 4} as a trimeric molecule with a centra
l cyclic Zn3P3 moiety in the twist-boat conformation. Bis(trimethylsil
yl)phosphido-n-butylzinc, that crystallizes in the orthorombic space g
roup Pbcn with {a = 1261.7(2); b = 2253.0(4); c = 1798.9(2) pm; Z = 4}
, shows a simular central Zn3P3 fragment. The stericially more demandi
ng trimethylsilylmethyl substituent leads to the formation of a dimeri
c molecule of (trimethylsilyl)phosphido-trimethylsilylmethylzinc {mono
klin, P2(1)/c; a = 907.2(4); b = 2079.8(8), c = 1070,2(3) pm; beta = 1
03,48(1)-degree; Z = 2}. Bis(trimethylsilyl)phosphido-iso-propylzinc s
hows in solution a temperatur-dependent equilibrium of the dimeric and
trimeric species; the crystalline state contains a 1:1 mixture of the
se two oligomers {orthorhombisch; Pbca; a = 1859.0(3); b = 2470.9(2);
c = 3450.7(3) pm; Z = 8}. The Zn-P bond lengths vary in a narrow range
around 239 pm, the Zn-C distances were found between 196 and 203 pm.