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Synthesis of the first Pentacarbonyltungsten(0) Complexes with P ‐Pentamethyl‐cyclopentadienyl‐substituted 1 H ‐Phosphirene Ligands: Crystal Structure of [{(Me 5 C 5 PC(H)=CPh}W(CO) 5 ]
Author(s) -
Streubel Rainer,
Bode Maren,
Schiemann Udo,
Wismach Cathleen,
Jones Peter G.,
Monsees Axel
Publication year - 2004
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200400045
Subject(s) - benzonitrile , chemistry , cyclopentadienyl complex , ring (chemistry) , crystal structure , crystallography , ligand (biochemistry) , tungsten , toluene , bond length , single crystal , alkyne , molecular geometry , stereochemistry , medicinal chemistry , molecule , catalysis , organic chemistry , biochemistry , receptor
The tungsten(0) complex [{Me 5 C 5 PC(Ph)=N}W(CO) 5 ] ( 1 ) reacts upon heating with alkyne derivatives 3a—e in toluene to form benzonitrile and the complexes [{Me 5 C 5 PC(R 1 )=C(R 2 )}W(CO)5] ( 4a—e ) ( 4a : R 1 = OEt, R 2 = H; 4b : R 1 = OEt, R 2 = SiMe 3 ; 4c : R 1 = Ph, R 2 = H; 4d : R 1 = Ph, R 2 = Ph; 4e : R 1 , R 2 = Et), which were purified by column chromatography (except 4d ). In reaction of 1 with 3d the tungsten(0) complex 5 , having a 2, 3‐dihydro‐1, 2, 3‐azadiphosphete ligand, is formed in a competing reaction. Spectroscopic and mass spectrometric data of complexes 4a — c, 4e and 5 are discussed. The structures of complexes 4c and 5 were determined by single‐crystal X‐ray diffraction In 4c the three‐membered ring has a C=C bond length of 1.312(3)Å and a C—P—C angle of 43.02(9)°. In 5 the P—P bond length is 2.2866(7)Å; the four‐membered ring is slightly folded (fold angle 15° about P1—C6).