ISSN:
0044-2313
Keywords:
Silanediyldiphosphinite
;
chelate complexes
;
synthesis
;
structure, multinuclear NMR spectroscopy
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Synthese eines neuen Silandiyldiphosphinits tBu2Si(OPPh2)2 und seine Reaktionen mit den Norbornadien-Komplexen C7H8M(CO)4 (M = Cr, Mo, W). Kristallstrukturen von cis-M(CO)4[tBu2Si(OPPh2)2] (M = Cr, Mo)Silandiyldiphosphinit tBu2Si(OPPh2)2 1 wurde dargestellt. 1 reagiert mit den Norbornadienkomplexen C7H8M(CO)4 (M = Cr, Mo, W) zu sechsgliedrigen Chelaten des Typs cis-M(CO)4[tBu2Si(OPPh2)2] 2-4. Die Kristallstrukturen des Chromkomplexes Cr(CO)4[tBuSi(OPPh2)2] 2 und des Molybdänkomplexes Mo(CO)4[tBuSi(OPPh2)2] 3 wurden bestimmt. Beide kristallisieren triklin (Raumgruppe P1) mit den Zellkonstanten: (2) a = 1 093(3) pm, b = 1 477(5) pm und c = 1 542(5) pm; α = 108.4(2)°, b̃ = 103.87(11)° und b̃ = 104.57(10)°; U = 2.143(12) nm3; Z = 2; (3) a = 1097.8(2) pm, b = 1 483.7(2) pm und c = 1 554.3(2) pm; α = 108.10(1)°, b̃ = 103.956(6)° und γ = 104.213(7)°; U = 2.1899(6) nm3; Z = 2. Beide Komplexe bestehen aus diskreten, leicht verdrillten oktaedrischen Monomeren mit annähernd planaren Chelatringen. Im Gegensatz hierzu wurde bei den Röntgenstrukturanalysen verwandter Komplexe Konformationen ermittelt, die von Twistboot zu „Chaiselongue“ variieren.
Notes:
Silanediyldiphosphinite tBu2Si(OPPh2)2 1 has been synthesised. 1 reacts with the norbornadiene complexes C7H8M(CO)4 (M = Cr, Mo, W) to give six-membered chelate rings of the type cis-M(CO)4[tBu2Si(OPPh2)2] 2-4. The crystal structures of the chromium and molybdenum complexes cis-Cr(CO)4[tBu2Si(OPPh2)2] 2 and cis-Mo(CO)4[tBu2Si(OPPh2)2] 3 have been determined. Both complexes crystallise in the triclinic system (space group P1) with unit cell parameters: (2) a = 1 093(3) pm, b = 1 477(5) pm and c = 1 542(5) pm; α = 108.4(2)°, b̃ = 103.87(11)° and b̃ = 104.57(10)°; U = 2.143(12) nm3; Z = 2; (3) a = 1 097.8(2) pm, b = 1 483.7(2) pm and c = 1 554.3(2) pm; α = 108.10(1)°, b̃ = 103.956(6)° and γ = 104.213(7)°; U = 2.1899(6) nm3; Z = 2. Both 2 and 3 consist of discrete, slightly distorted, octahedral monomers in which the six-membered chelate rings are essentially planar. In contrast, the conformations of the chelate rings found in crystal structures of analogous complexes vary from twist-boat to “chaise longue”.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19956210433
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