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Early Transition Metal Complexes of Triphosphorus Macrocycles
Author(s) -
Baker Robert J.,
Davies Philip C.,
Edwards Peter G.,
Farley Robert D.,
Liyanage Sudantha S.,
Murphy Damien M.,
Yong Ben
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(200208)2002:8<1975::aid-ejic1975>3.0.co;2-i
Subject(s) - chemistry , electron paramagnetic resonance , adduct , moiety , transition metal , halide , nuclear magnetic resonance spectroscopy , metal , crystallography , metal halides , ligand (biochemistry) , spectroscopy , polymer chemistry , stereochemistry , inorganic chemistry , organic chemistry , catalysis , biochemistry , physics , receptor , nuclear magnetic resonance , quantum mechanics
The reactions of 1,5,9‐triethyl‐1,5,9‐triphosphacyclododecane, [12]aneP 3 Et 3 , with first‐row transition metal halides MCl 3 [M = Ti ( 1 ), V ( 2 ), and Cr ( 3 )] or their THF adducts are reported. The oxidation of 2 gives the complex ([12]aneP 3 Et 3 )V(O)Cl 2 ( 4 ). This is the first example of a phosphane ligand that is trans to a vanadyl moiety. Also reported are V III ( 5 ) and Cr III ( 6 ) complexes of the pendant ether macrocycles [12]aneP 3 (C 2 H 4 OEt) 3 and 12[ane]P 3 (C 3 H 6 OMe) 3 respectively. The complexes 1 − 6 have been characterised crystallographically and represent a rare class of phosphane complexes of these metals. The paramagnetic d 1 compounds are characterised by EPR and ENDOR spectroscopy, simulation of which gives valuable structural information of these species in frozen solution. With [12]aneP 3 Et 3 , Nb III and Nb IV chlorides give air‐sensitive materials which could not be fully characterised although by comparison with compound 4 , EPR and ENDOR spectroscopy indicate the principal oxidation product to be ([12]aneP 3 Et 3 )Nb(O)Cl 2 ( 7 ). (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)