Unusual molecular hydrogen complex of rhenium: a long hydrogen-hydrogen bond and inertness to substitution

• Published in: Journal of the American Chemical Society Vol. 112; no. 7; pp. 2798 - 2800
• Main Authors: Kim, Youhyuk, Deng, Haibin, Meek, Devon W, Wojcicki, Andrew
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 01.03.1990
• Subjects: 400201 - Chemical & Physicochemical Properties; CHEMICAL BONDS; COMPLEXES; Condensed matter: structure, mechanical and thermal properties; DATA; DATA ANALYSIS; Exact sciences and technology; EXPERIMENTAL DATA; INFORMATION; Inorganic compounds; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; MEASURING METHODS; Metal complexes; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANOMETALLIC COMPOUNDS; Physics; RHENIUM COMPLEXES; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; SYNTHESIS; TRANSITION ELEMENT COMPLEXES; Inorganic ligand; Molecular structure; Hydrogen Molecules; Organic phosphine; Organic ligand; Transition metal Complexes; Experimental study; X ray diffraction; Hydrido complex; Tritertiary phosphine; Rhenium Complexes; Intramolecular hydrogen bond; Crystalline structure
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja00163a050

Since the discovery of M(H{sub 2})(CO){sub 3}(PR{sub 3}){sub 2} (M = Mo, W; R = i-Pr or Cy) by Kubas and co-workers, transition-metal polyhydrido complexes have been the subject of intensive research and close scrutiny with respect to the nature of metal-hydrogen bonding, e.g., M-(H){sub 3} (classical), H-M-(H{sub 2}) (nonclassical), or possibly M-(H{sub 3}). In this context, the question of the bonding in the rhenium pentahydrides ReH{sub 5}L{sub 3} has been particularly intriguing, since initially {sup 1}H NMR (T{sub 1} values) and x-ray results pointed to different conclusions when L = PPh{sub 3}. Here the authors report that protonation of an analogous rhenium pentahydride containing a tridentate phosphine ligand, viz., ReH{sub 5}(Cyttp) (1, Cyttp = PhP(CH{sub 2}CH{sub 2}CH{sub 2}PCy{sub 2}){sub 2}), affords an unusual dihydrogen complex, (Re(H{sub 2})H{sub 4}(Cyttp))SbF{sub 6} (2).