Synthesis of electron-rich platinum centers: Platinum0(carbene)(alkene)2 complexes |
| |
| Affiliation: | 1. Van ‘t Hoff Institute of Molecular Sciences, Molecular Inorganic Chemistry, Universiteit van Amsterdam, Nieuwe Achtergracht 166, 1018 WV Amsterdam, The Netherlands;2. Bijvoet Center for Biomolecular Research, Vakgroep Kristal- en Struktuurchemie, Utrecht University, Padualaan 8, NL-3584 CH Utrecht, The Netherlands;1. School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, People''s Republic of China;2. Xi’an Aerospace Propulsion Test Technique Institute, Xi’an 710100, People''s Republic of China;1. Department of Medicinal and Applied Chemistry, Drug Development and Value Creation Research Center, Kaohsiung Medical University, Kaohsiung 807, Taiwan;2. Department of Chemistry, National Institute of Technology, Tiruchirappalli 620 015, India;3. Department of Medical Research, Kaohsiung Medical University Hospital, Kaohsiung Medical University, Kaohsiung 807, Taiwan;4. Department of Chemistry, National Sun Yat-Sen University, Kaohsiung 804, Taiwan |
| |
| Abstract: | The synthesis and molecular structure of the zero-valent platinum-mono-carbene-bis-alkene complexes [Pt0(NHC)(dimethyl fumarate)2] (NHC = 1,3-dimesityl-imidazol-2-ylidene (1a); 1,3-dimesityl-dihydroimidazol-2-ylidene (2a); diphenyl-dihydroimidazol-2-ylidene (2b) are described. Two routes have been evaluated for the synthesis of 1a and 2a, involving reaction of a zero-valent platinum compound either with an isolated carbene ligand, or with an in situ generated carbene ligand. The in situ method proved to be easier and gave similar yields of about 50% after crystallization. Attempts have been made to synthesize similar compounds with N-phenyl and N-alkyl groups, of which the latter met with little success. However, (1,3-diphenyl-dihydroimidazol-2-ylidene)-bis(η2-dimethyl fumarate) platinum(0) (2b) could be obtained in 49% yield, after crystallization, from the appropriate Wanzlick dimer.Compound 1a reacts with H2 and D2 in sequences of oxidative addition, migration–insertion involving dimethyl fumarate, and reductive elimination to form neutral hydrido platinum (II) carbene complexes, probably containing a metallacyclic (R)–C O … Pt unit. |
| |
| Keywords: | |
| 本文献已被 ScienceDirect 等数据库收录！ |
|
