Alan R. Cutler Professor Organometallics Cogswell 103 518.276.8447 cutlea@rpi.edu

Alan Cutler received his Ph.D. in organic and transition organometallic chemistry at Brandeis University. Postdoctoral studies with David Dolphin (Harvard University and the University of British Columbia) and Richard Holm (Stanford University) rounded out his interests in bio-inorganic and inorganic chemistry. Dr. Cutler joined the RPI chemistry faculty in 1982.

Carbonylation Chemistry

We are synthesizing poly(alkoxymethylene)acyl ligands that derive from carbon monoxide and retain an oxygen functionality at each carbon center. These transition organometallic acyl complexes result from repeating a three-step sequence of ligand reactions: (a) electrophilic activation of an acyl ligand, (b) hydride transfer to its oxycarbenoid derivative, and (c) carbonylation of the resulting a-alkoxyalkyl ligand. Catalytic hydrosilation of organometallic acyl complexes, combining steps a&b (E-H = R3Si-H), offers an unusually mild and selective procedure for reducing the acyl ligand. Coupling this hydrosilation reaction with a subsequent carbonylation step c will afford the corresponding poly(siloxymethylene)acyl compounds.

Catalytic Hydrosilation and Hydrometalation

We propose to synthesize examples of poly(metallomethylene) and poly(metalloethylene)acyl compounds. The catalytic hydrosilation reactions of transition metal acyl complexes that we recently have developed are being extended to the stepwise synthesis of carbosilane and metal-containing oligomers in which all carbon centers derive from carbon monoxide.

CO2 Fixation

Heterobimetallic m(n1-C: n2-O,O')CO2 complexes LxM-CO2-M'Ly feature synergistic CO2 binding in which an electron-rich metal system (e.g., LxM = Cp(CO)2Ru) contributes (n1-C) metallocarboxylate binding and an oxophilic system (LyM' = Zr(Cl)Cp2) sequesters one or both metallocarboxylate oxygens. We are establishing the ligand reactions for reducing CO2 to formaldehyde (or methanol), which we will then optimize and combine into a catalytic system.

C. C. Tso and A. R. Cutler, "Electrophilic Activation, Reduction, and Carbonylation of the Acetyl Ligand on (PPh3)(CO)3CoCOCH3" Polyhedron, 1993.

D. L. Tarazano, T. W. Bodnar and A. R. Cutler, "Synthesis and Solution Dynamics of [Cp(CO)2Fe]2(CH=CH2)+PF6-, a m-(h1:h2) Vinyl Complex Not Containing a Metal-Metal Bond" J. Organometallic Chem.

B. T. Gregg and A. R. Cutler, "Reactivity of Cobalt Acetyl Complexes (PR3)(CO)3CoCOCH3 with Monohydrosilanes" Organometallics, 11, 4276 (1992).

A. B. Todaro, L. D. Tarazano, A. R. Cutler and J. J. Benoit, "(h5-C5H5)(CO)Fe(CH3CN)2+ as a Synthetic Intermediate in Preparing Disubstituted Compounds (h5-C5H5)(CO)Fe(L1)(L2)" J. Organometallic Chem.