Synthesis and Reactivity of Group 6 Metal Carbonyl Complexes with Bis(pyrazol-1-yl)methanes Modified by the Vinyltin Groups

• Published in: Chinese journal of chemistry Vol. 27; no. 5; pp. 993 - 998
• Main Authors: WEN, Zhenkang, YANG, Zhi, SONG, Haibin, TANG, Liangfu
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.05.2009; WILEY‐VCH Verlag; Wiley
• Subjects: bis(pyrazol-1-yl)methane; Chemistry; Chemistry, Multidisciplinary; group 6 metal carbonyl complex; heterobimetallic complex; Physical Sciences; Science & Technology; vinyltin; HALIDES; vinyltin; MULTIDENTATE LIGANDS; TUNGSTEN; CRYSTAL; heterobimetallic complex; METHINE CARBON; bis(pyrazol-1-yl)methane; DERIVATIVES; OLEFIN; group 6 metal carbonyl complex
• ISSN: 1001-604X; 1614-7065
• DOI: 10.1002/cjoc.200990169

Diphenyl(vinyl)stannylbis(3,5‐dimethylpyrazol‐1‐yl)methane and diphenyl(vinyl)stannylbis(3,4,5‐trimethyl‐ pyrazol‐1‐yl)methane have been synthesized by the reaction of bis(3,5‐dimethylpyrazol‐1‐yl)methyl or bis(3,4,5‐ trimethylpyrazol‐1‐yl)methyllithium with diphenyl(vinyl)tin iodide. Treatment of these bis(pyrazol‐1‐yl)methanes modified by the vinyltin groups with M(CO)5THF (M=Mo and W) in refluxing THF resulted in new heterobimetallic complexes R3SnCHPz2M(CO)3 (R3Sn represents trivinyltin or diphenyl(vinyl)tin, and Pz represents substituted pyrazol‐1‐yl), in which a vinyl group bonds to the molybdenum or tungsten atom in η2‐fashion to lead to bis(pyrazol‐1‐yl)methanes acting as a tridentate κ3‐(π,N,N) ligand. Reaction of (CH2=CH)3SnCH(3,5‐Me2Pz)2W(CO)3 and Ph2(CH2=CH)SnCH(3,5‐Me2Pz)2W(CO)3 with I2 has been investigated. The former gave a complex CH2(3,5‐Me2Pz)2W(CO)4, while the latter yielded a four‐membered heterometallocyclic complex CH(3,5‐Me2Pz)2W(CO)3I with the loss of the organotin group. Treatment of this four‐membered heterometallocyclic complex with PhSNa led to the iodide anion replaced by the thiophenolate anion to give a complex CH(3,5‐Me2Pz)2W(CO)3SPh. Bis(pyrazol‐1‐yl)methane ligands with the vinyltin groups on the methine carbon have been synthesized and their related reactions with M(CO)5THF (M=Mo and W) have been investigated.