A Coordination Chemist's View of Surface Science

Abstract

Structure, a necessary element for an understanding of chemistry, has not been precisely defined, in molecular detail, for the surface species formed at a solid-gas interface. Dramatic advances in theory, instruments and experimental procedures have now provided the surface scientists with an impressive arsenal of structural and electronic probes. Chemistry in the form of the classic displacement reaction can also provide an insight to the structure of surface compounds. In fact, many of the experimental procedures and systematics of the coordination and organometallic chemist can be effectively utilized in a complementary fashion with surface physics techniques to gain a more definitive picture of chemisorption states and or reactions at a surface.

Molecular Metal Clusters as Catalysts

“…of H 2 per mole of cluster, equations (3) and (4). There was no evidence 18 of a mononuclear species in this hydrogen reaction system.…”

Coordination chemistry of metal surfaces and metal complexes

“…Interestingly, this cluster has not been prepared directly from the nitrile but by an indirect two-step synthesis outlined in equations 2 and 3 below: HFe3(CO)11 + RCN(moist)-HFe3(CO)g(HN=CR) (2) HFe3(CO) g(HN=CR) OXLOI' Fe3(C0) g(NCR) (3) This structurally defined cluster (10) Alkyl isocyanides are relatively strong field ligands in transition metal chemistry; the molecules are both good c donor and it acceptor ligands and typically the isocyanides readily displace carbon monoxide from mononuclear or polynuclear metal carbonyl complexes. Since methyl isocyanide is strongly bound on both the Ni(lll) and Pt(lll) surfaces, the thermochemical features of CH3CN and CH3NC chemisorption on these surfaces are fully analogous to that of molecular coordination compounds.…”

“…Our research addresses the intimate structural and stereochemical features of the interactions and reactions of molecules withmetal atoms constrainedat the surfaces of metals and within molecular mononuclearand pôlynuclear metal complexes (1,2). I believe that there is a fundamental set of coordination chemistry principles applicable to all metal complex and all metal chemistry; there should be no.…”

Metal cluster chemistry: Structure and stereochemistry in the polynuclear rhodium hydrides H n Rh n [P(OR) 3 ] 2n

“…Discrete molecular metal clusters can be considered as simple models of metal surface coordination chemistry (1)(2)(3)(4)(5)(6)(7)(8). This modeling approach can yield information about structure, ligand migration, chemistry, and catalytic chemistry that may be of substantive value in the analysis of metal surface chemistry (7,8).…”

“…This modeling approach can yield information about structure, ligand migration, chemistry, and catalytic chemistry that may be of substantive value in the analysis of metal surface chemistry (7,8). One limitation in this formal analogy is the tendency of some molecular clusters to fragment into mononuclear metal complexes in chemical and catalytic reactions.…”