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Syntheses and Characterization of Molybdenum Complexes with the (1,3‐Dithioliumyl)diphenylphosphine Containing Ligands
Author(s) -
Yih KuangHway
Publication year - 1999
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.199900072
Subject(s) - chemistry , protonation , diphenylphosphine , deprotonation , molybdenum , medicinal chemistry , intramolecular force , halide , alkylation , sulfur , stereochemistry , phosphine , ion , inorganic chemistry , organic chemistry , catalysis
Treatment of [Et 4 N][Mo(CO) 5 (PPh 2 CS 2 )], 1 with unsaturated organic halides afforded the neutral complexes Mo(CO) 5 (PPh 2 CS 2 R) (R = CH 2 CN, 2 ; R = CH 2 C≡CH, 3 ). Alkylation reactions take place at the sulfur atom. Protonation of complex 2 and 3 with HBF 4 produced the intramolecular cyclization products [Mo(CO) 5 (PPh 2 CS 2 C 2 H 3 N)][BF 4 ], 4 and [Mo(CO) 5 (PPh 2 CS 2 C 3 H 4 )][BF 4 ], 5 , respectively. In complex 4 and 5 , two five‐membered 1,3‐dithiolium rings formed. Protonation of 3 to 5 is not reversible, but deprotonation of 4 by n ‐BuLi or PPh 3 gave 2 quantitatively. Treatment of 4 with n ‐Bu 4 NF yielded complex Mo(CO) 5 PPh 2 F, 6 and 2 with 1:1 ratio, but in the reaction of 5 and n ‐Bu 4 NF only compound 6 was formed. All of these complexes are identified by spectroscopic methods.