Andreas Mayr

Inorganic and Organometallic Chemistry

Reactivity of Transition Metal-Carbon Multiple Bonds

A major project of my group is concerned with the reactivity of metal-carbon multiple bonds. The long-range goal is the development of selective bond-forming processes. Our work is focusing on transition metal alkylidyne complexes, i. e. compounds containing metal-carbon triple bonds. In recent years, we studied coupling reactions of alkylidyne ligands with other terminal ligands such as carbonyl, isocyanide, and thiocarbonyl ligands. The coupling of two alkylidyne ligands was also demonstrated. Coupling reactions of alkylidyne ligands with other ligands such as alkylidene, imido, oxo, alkyl, aryl, alkynyl ligands will be explored. In this work, we are primarily interested in the fundamental aspects of the bond-forming steps. The potential of low-valent transition metal alkylidyne complexes as reagents in organic synthesis is only beginning to be realized. In an effort to establish a rational basis for the development of this chemistry, we investigate reactions of alkylidyne metal complexes with alkenes, alkynes and other unsaturated organic substrates. These reactions are useful for the construction of larger organic systems within the coordination sphere of transition metal centers.

Metal-Carbon Multiple Bonds as Functional Components in Molecular Materials

Metal-carbon triple bonds provide a means of strong electronic coupling between metal centers and organic p systems. This feature and the presence of low-energy metal-to-alkylidyne charge transfer transitions make metal-carbon triple bonds promising as components in molecular materials. Furthermore, metal-carbon triple bonds are thermally rather stable entities, and reliable synthetic methods are available to fine-tune the electronic properties of metal alkylidyne complexes. Several functionalized tungsten alkylidyne complexes of the Fischer-type have been designed for the study of the following aspects: nonlinear optical properties, photo-induced directional electron transfer, and photo-induced energy transfer. Modifications of the systems to form liquid crystals are being explored

Synthesis of Molecular Solid-State Materials by the Self-Assembly of Stable Transition Metal Complex Building Blocks

A new project in our group is concerned with the synthesis of molecular materials based on the assembly of stable transition metal complex building blocks. The basic synthetic strategy is based on the use of special bi- (or multi-) functional ligands. One functionality is a strongly ligating site. It is used to form the stable transition metal complex building blocks of defined geometry and size. The other function is a site capable of weak interactions, such as a weakly coordinating site or a hydrogen bonding site. The building blocks are interconnected in a geometrically defined manner via the weak interaction sites. The goal is to achieve control over the supramolecular structures and physical properties on the new materials via the nature of these transition metal complex building blocks. Thus by proper choice of transition metal centers (electron configuration and coordination geometry) and spacer ligands (length, steric and electronic properties) it may be possible to determine the dimensions of the new materials and influence their electronic properties. Presently, we are focusing on the use of transition metal complexes of bifunctional isocyanides as the building blocks.

Raman and infrared spectra and pressure tuning Raman and infrared spectra of multinuclear metal carbyne complexes. Xu ZH, Mayr A, Butler IS. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 648 (1-2): 93-98 APR 1 2002

Raman and infrared spectral studies of tungsten organometallic carbyne complex at high external pressure. Xu ZH, Mayr A, Butler IS. SPECTROSCOPY AND SPECTRAL ANALYSIS, 21 (5): 596-598 OCT 2001

Infrared and Raman spectra studies on isomultinuclear organometallic carbyne compounds. Xu ZH, Mayr A.SPECTROSCOPY AND SPECTRAL ANALYSIS, 20 (5): 702-703 OCT 2000

Syntheses and solid-state structures of molecular and extended silver(I) complexes of 4-isocyano-3,5-diisopropylbenzonitrile. Li MX, Cheung KK, Mayr A.JOURNAL OF SOLID STATE CHEMISTRY, 152 (1): 247-252 JUN 2000

Oxidatively induced insertion of an alkylidyne unit into the tungsten tris(pyrazolyl)borate cage.Mayr A, Ahn S. INORGANICA CHIMICA ACTA, 300: 406-413 APR 30 2000

Development of a T-joint for covalent molecular construction based on 2,2 '-bipyridine and phenanthroline isocyanide metal complexes. Dong YB, Yang LQ, Cheung KK, Mayr A.JOURNAL OF ORGANOMETALLIC CHEMISTRY, 598 (1): 55-62 MAR 25 2000

Synthesis of several functionalized cis-diisocyanide and fac-triisocyanide metal complexes. Yang LQ, Cheung KK, Mayr A.JOURNAL OF ORGANOMETALLIC CHEMISTRY, 585 (1): 26-34 AUG 1 1999

Unsaturated alkylidyne ligands bearing a terminal isocyanide functionality and intervening ethynylbenzene groups. Mayr A, Yu MPY. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 577 (2): 223-227 APR 1 1999

Electronic communication between metal centers across unsaturated alkylidyne ligands. Mayr A, Yu MPY, Yam VWW. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 121 (8): 1760-1761 MAR 3 1999

Metal complexes of pyridylphenylisocyanides and pyridylethynylphenylisocyanides as building blocks for coordination polymers and supramolecular assemblies.Mayr A, Guo JH. INORGANIC CHEMISTRY, 38 (5): 921-928 MAR 8 1999

Synthesis of transition metal isocyanide complexes containing hydrogen bonding sites in peripheral locations. Lau KY, Mayr A, Cheung KK. INORGANICA CHIMICA ACTA, 285 (2): 223-232 FEB 15 1999

Synthesis and formation of metal complexes of 4-alkynyl and 4-cyano-2,6-diisopropylphenylisocyanides. Lu ZL, Mayr A, Cheung KK. INORGANICA CHIMICA ACTA, 284 (2): 205-214 JAN 30 1999

Cyanoisocyanoarene metal complexes as building blocks for coordination polymers: Structural nonrigidity of a metal-nitrile linkage. Mayr A, Mao LF. INORGANIC CHEMISTRY, 37 (22): 5776-5780 NOV 2 1998

Protonation of Fischer-type alkylidyne carbonyltungsten complexes. Structural comparison of alkylidyne and alkylidene metal complexes, including a neutron diffraction study of [W(CHCH3)Cl-2(CO)(PMe3)(2)]. Bastos CM, Lee KS, Kjelsberg MA, Mayr A, Van Engen D, Koch SA, Franolic JD, Klooster WT, Koetzle TF. INORGANICA CHIMICA ACTA, 279 (1): 7-23 SEP 15 1998

Mesogenic palladium and platinum-diiodide complexes of 4-isocyanobenzylidene-4-alkoxyphenylimines. Wang SX, Mayr A, Cheung KK. JOURNAL OF MATERIALS CHEMISTRY, 8 (7): 1561-1565 JUL 1998

Electronic communication between metal centers across unsaturated alkylidyne ligands. Yu MPY, Mayr A, Yam VWW, Cheung KK. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 215: 043-INOR Part 1 APR 2 1998

Transition metal complexes of isocyanides as precursors for molecular solids. Mao LF, Guo JH, Lau KY, Mayr A.ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 215: 493-INOR Part 1 APR 2 1998

Synthesis and characterization of some transition metal complexes of alkylisocyanobenzoates. Squires ME, Mayr A.INORGANICA CHIMICA ACTA, 264 (1-2): 161-169 NOV 1 1997

Transition metal complexes of isocyanopyridines, isocyanoquinolines and isocyanoisoquinolines. Guo JH, Mayr A.INORGANICA CHIMICA ACTA, 261 (2): 141-146 SEP 15 1997

Fischer-type alkylidyne tungsten complexes containing strong pi donor ligands.Mayr A, Lee TY. INORGANICA CHIMICA ACTA, 252 (1-2): 131-139 NOV 1 1996

Transition metal isocyanide complexes as precursors for organometallic supramolecules. Guo JH, Mayr A.
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 212: 273-INOR Part 1 AUG 25 1996

Transition metal complexes of cyano-isocyanoarenes as building blocks for one-, two-, and three-dimensional molecular solids. Mao LF, Mayr A.ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY 212: 274-INOR Part 1 AUG 25 1996

Tungsten tris(pyrazolyl)borate cage expansion by formal insertion of an alkylidyne group into a tungsten-nitrogen bond. Ahn S, Mayr AJOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 118 (31): 7408-7409 AUG 7 1996

Transition metal complexes of cyanoisocyanoarenes as building blocks for one-, two-, and three-dimensional molecular solids. Mao LF, Mayr A.INORGANIC CHEMISTRY, 35 (11): 3183-3187 MAY 22 1996