Displacement of norbornadiene (NBD) from Pt(CF3)2(NBD) by weak donor ligands L, and reactions of cis-Pt(CF3)2L2 with water and acids

Appleton T.G., Berry R.D., Hall J.R. and Neale D.W. (1989) Displacement of norbornadiene (NBD) from Pt(CF3)2(NBD) by weak donor ligands L, and reactions of cis-Pt(CF3)2L2 with water and acids. Journal of Organometallic Chemistry, 364 1-2: 249-273. doi:10.1016/0022-328X(89)85349-5


Author Appleton T.G.
Berry R.D.
Hall J.R.
Neale D.W.
Title Displacement of norbornadiene (NBD) from Pt(CF3)2(NBD) by weak donor ligands L, and reactions of cis-Pt(CF3)2L2 with water and acids
Journal name Journal of Organometallic Chemistry   Check publisher's open access policy
ISSN 0022-328X
Publication date 1989-03-28
Sub-type Article (original research)
DOI 10.1016/0022-328X(89)85349-5
Volume 364
Issue 1-2
Start page 249
End page 273
Total pages 25
Subject 1303 Specialist Studies in Education
1501 Accounting, Auditing and Accountability
1604 Human Geography
1605 Policy and Administration
1606 Political Science
2501 Materials Science (miscellaneous)
2505 Materials Chemistry
Abstract The NBD ligand in Pt(CF3)2(NBD) has been replaced under mild conditions by a number of neutral S-, N-, and O-donor ligands to form cis-Pt(CF3)2L2 complexes (L2 = N,N,N′,N′-tetramethylethylenediamine (tmen), bipyridine (bipy), ethylenediamine (en); L = pyridine (py), NH3, dimethylsulfoxide (DMSO), CH3CN, C6H5CN, N,N-dimethylformamide (DMF)). Reaction with DMSO produces predominantly the isomer cis-Pt(CF3)2(DMSO-S)(DMSO-O), with cis-Pt(CF3)2(DMSO-S)2 a minor component, as a result of steric constraints. Water or methanol attacks the CF3 groups, producing fluoride ion. The fluorine atoms of cis-Pt(CF3)2L2 (L2 = bipy, tmen; L = py) are susceptible to electrophilic attack by H+. Reaction with aqueous HCl or HClO4 converts one CF3 group into a coordinated CO group. With HCl, simultaneous protonation and displacement of the N-donor ligands occurred, yielding cis-Pt(CF3)(CO)Cl2 -. With HClO4, the complexes cis-Pt(CF3)(CO)L2 + are initially generated, with subsequent displacement of the tmen and py (but not bipy) ligands to form cis-Pt(CF3)(CO)(OH2)2 +. The remaining CF3 group is not attacked by H+. Reaction of Pt(CF3)2(NBD) with halide ions in acetone initially produced the binuclear complexes [(CF3)2Pt(μ-X)2Pt(CF3)2]2- (X = I, Cl) containing bridging halide. With larger amounts of halide ion the expected cis-Pt(CF3)2X2 2- complexes were not obtained, and instead cis-Pt(CF3)(CO)X2 - and fluoride ion were formed. When the complexes [(CF3)2Pt(μ-X)2Pt(CF3)2]2- were kept in the presence of NBD, cis-Pt(CF3)(CO)X2 - and Pt(CF3)2(NBD) were formed. When X = I, these two complexes then reacted together to yield cis-Pt(CF3)2I(CO)- and Pt(CF3)I(NBD).
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown

Document type: Journal Article
Sub-type: Article (original research)
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