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Acyl and α‐Ketoacyl Complexes of Pt(II) with Weak Donor Ligands
Author(s) -
Chen JwuTing,
Yeh YuSung,
Tzeng WenHwa,
Huang TsangMiao,
Cheng MingChu,
Lee GeenHsiang,
Wang Yu
Publication year - 1991
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.199100094
Subject(s) - chemistry , ligand (biochemistry) , trifluoromethanesulfonate , cationic polymerization , medicinal chemistry , decarbonylation , stereochemistry , yield (engineering) , crystal structure , crystallography , catalysis , polymer chemistry , organic chemistry , biochemistry , materials science , receptor , metallurgy
Treatment of trans‐Pt(COCOPh)(Cl)(PPh 3 ) 2 (1a) with AgBF 4 in THF led to the formation of a metastatic complex trans‐[Pt(COCOPh)(THF)(PPh 3 ) 2 ](BF 4 ) (2) which readily underwent ligand substitution to give a cationic aqua complex trans‐[Pt(COCOPh)(OH 2 )(PPh 3 ) 2 ](BF 4 ) (5a). Complex 5a has been characterized spectroscopically and crystallographically. Analogous reaction of trans‐ Pt(COCOOMe)(Cl)(PPh 3 ) 2 (1b) with Ag(CF 3 SO 3 ) in dried CH 2 C1 2 was found first to yield a methoxyoxalyl triflato complextrans‐Pt(COCOOMe)(OTf)(PPh 3 ) 2 (6). Attempts to crystallize the triflato product in CH 2 ‐cl 2 hexane under ambient conditions also afforded an aqua complex of the triflate salt f/wu‐[Pt(COCOOMe)(OH 2 )(PPhj) 2 ](CF 3 SO 3 ) (5b). Complex 5a in a noncoordinating solvent such as CH 2 C1 2 or CHCl 3 suffered spontaneous decarbonylation to form first cis‐[Pt(COPh)(CO)(PPh 3 ) 2 l(BF 4 ) (3a) then the thermodynamically stable isomer trans‐[Pt(COPh)(CO)(PPh 3 ) 2 ](BF 4 ) (3b). Crystallization of complex 3b under ambient conditions resulted in an aqua benzoyl complex trans‐ [Pt(COPh)(OH 2 )(PPh 3 ) 2 ](BF 4 ) (7). The replacement of the H 2O ligand in complex 7 by CO was done simply by bubbling CO into the solution of 7. The single crystal structures of 5b and 7 have been determined by X‐ray diffraction. The distances of the Pt‐O bonds in 5a, 5b, and 7 support that the aqua ligand is a weak donor in such cationic aquaorganoplatinum(lI) complexes, in agreement with their lability to the substitution reactions.