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P−H Activation By Zirconium Amido Complexes: From New Phosphanidozirconium Complexes to the First Zr 2 P 6 Cluster with the [RP−P−PR] 3− Ligand [R = Me 2 ( i PrMe 2 C)Si]
Author(s) -
Driess Matthias,
Aust Joachim,
Merz Klaus
Publication year - 2002
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200211)2002:11<2961::aid-ejic2961>3.0.co;2-r
Subject(s) - chemistry , yield (engineering) , zirconium , ligand (biochemistry) , crystallography , intermolecular force , cluster (spacecraft) , derivative (finance) , ring (chemistry) , tris , salt (chemistry) , stereochemistry , inorganic chemistry , molecule , organic chemistry , biochemistry , materials science , receptor , computer science , economics , financial economics , metallurgy , programming language
A new, efficient and salt‐free method to synthesize phosphanidozirconium complexes is reported. Treatment of [Cp 2 Zr(PHR) 2 ] 3 [R = Me 2 ( i PrMe 2 C)Si] with [Zr(NEt 2 ) 4 ] furnishes the first unsymmetrically substituted 1,3‐dizircona‐2,4‐diphosphetane [Cp 2 Zr(PR) 2 Zr(NEt 2 ) 2 ] ( 1 ; Cp = η 5 ‐C 5 H 5 ) in quantitative yield, which undergoes intermolecular ligand exchange reactions at 140 °C to form the mixed substituted derivative [Cp 2 Zr(PR) 2 ZrCp(NEt 2 )] ( 2 ) in 28% yield. An X‐ray diffraction analysis of 2 revealed that the four‐membered Zr 2 P 2 ring is only slightly puckered. The Brønsted acid‐base reaction of [Cp*Zr(NMe 2 ) 3 ] ( 4 ; Cp* = C 5 Me 5 ) with the P−H acidic silylphosphane RPH 2 affords the corresponding tris(phosphanido) complex [Cp*Zr(PHR) 3 ] ( 5 ) in the form of a red‐brown oil in quantitative yield. Heating of the latter at 140 °C leads to the first dinuclear zirconium phosphanide cluster [(Cp*Zr) 2 (R 2 P 3 ) 2 ] ( 6 ), which has been isolated in the form of dark green crystals in 12% yield and structurally characterized by X‐ray diffraction analysis. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)