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Dinuclear Molybdenum(III) and Tungsten(III) Calix[4]arene Complexes − Metal‐Metal Triple Bonds Supported by Bridging Calix[4]arene Ligands
Author(s) -
Radius Udo,
Attner Juri
Publication year - 1998
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/(sici)1099-0682(199803)1998:3<299::aid-ejic299>3.0.co;2-q
Subject(s) - chemistry , deprotonation , molybdenum , crystallography , metal , ligand (biochemistry) , tungsten compounds , stereochemistry , tungsten , calixarene , transition metal , crystal structure , bridging ligand , triple bond , molecule , polymer chemistry , inorganic chemistry , double bond , organic chemistry , ion , biochemistry , receptor , catalysis
Addition of p ‐ tert ‐butylcalix[4]arene LH 4 to the dinuclear compounds M 2 (NMe 2 ) 6 (M = Mo, W) results in the formation of [NH 2 Me 2 ] 2 [L 2 M 2 ] 1 (M = Mo) and 2 (M = W). Both compounds have been characterized by spectroscopic methods and single‐crystal X‐ray diffraction. The metal−metal distances of 1 and 2 , of 2.194(1) Å and 2.293(1) Å, respectively, are consistent with the retention of the M≡M triple bond. Both „ate” complexes contain a [M≡M] 6+ dimetal core, supported by two bridging μ 2 ‐κ 2 O,κ 2 O‐calix[4]arene ligands in the solid state. These compounds are the first examples of a formally fourfold deprotonated calix[4]arene acting as a μ 2 ‐κ 2 O,κ 2 O bridging ligand for two transition metal centres. The calix[4]arenes in 1 and 2 are distorted from a cone conformation in the uncomplexed ligand, to an elliptical cone section. 1 H‐NMR data at variable temperatures suggest fluxional behaviour of 1 and 2 in solution.