Nancy M. Golembeski

Syntheses and Reactivity of Organohletallic Cohlpounds Containing Ihlinoacyl Ligands. Reactions of Hletal Carbonyl Anions with Ihlidoyl Halides

Abstract Metal carbonyl anions readily react with imidoyl halides through nucleophilic displacement of the halide atom to produce complexes containing η1-iminoacyl ligands. However, weakly nucleophilic anions, such as tetracarbonylcobaltate, induce a head-to-tail coupling reaction of two imidoyl groupings via the incorporation of two anions. This has been established by an X-ray crystallographic analysis of the compound CO2(CO)5(P(CH3)2C6H5)[(C6H5)CN(C6H5)]2. The bis-imidoyl ligand chelates one cobalt atom while one of the carbon atoms bridges the two mutually bonded cobalt atoms. Photolytic decarbonylation of the complexes containing η1-iminoacyl ligands may proceed by either of three processes. When the substituent on the nitrogen atom is an alkyl group, either a migration with formation of an isocyanide ligand or formation of an η2-iminoacyl ligand can occur. When the substituent is an aryl group, ortho-metallation of the N-aryl ring occurs. This has been demonstrated by an X-ray crystallographic analysis of the compound (C5H5)Fe-(CO)[C(C6H5)N(H)p-CH3C6H3)] which contains a phenyl-N-p-tolylaminocarbene ligand in which the p-tolyl ring is bonded to the iron atom in an ortho position.

The synthesis and crystal and molecular structure of H3(μ-η2-C6H4)(μ-η2-HC3NC6H5)Os3(CO)8

Abstract The complex H 3 (μ-η 2 -C 6 H 4 ) (μ-η 2 -HC 3 NC 6 H 5 )Os 3 (CO) 8 has been synthesized and characterized by IR, 1 H NMR and X-ray crystal structure analyses. The compound contains a dihapto -benzyne ligand bridging one edge of a triangular cluster of osmium atoms and a dihapto -formimidoyl ligand bridging a different edge on the opposite face of the cluster from the benzyne ligand.

Syntheses of organometallic compounds containing iminoacyl ligands. Reactions of metal carbonyl anions with imidoyl halides

Abstract Reactions of metal carbonyl anions with imidoyl halides provide a convenient route for the preparation of organometallic complexes containing both η 1 - and η 2 -iminoacyl ligands. With poorer nucleophiles such as tetracarbonyl cobaltate anion, coupling of imidoyl groupings becomes important. This is illustrated by the molecules Co 2 (CO) 5 (P(CH 3 ) 2 C 6 H 5 ){(C 6 H 5 )CN(C 6 H 5 )} 2 which has been crystallographically analyzed.

Triosmium cluster compounds containing isocyanide and hydride ligands. Crystal and molecular structure of (. mu. -H)(. mu. -eta/sup 1/-C==N(H)(t-C/sub 4/H/sub 9/))Os/sub 3/(CO)/sub 10/

The crystal and molecular structure of the compound (..mu..-H)(..mu..-eta/sup 1/-C==N(H)(t-C/sub 4/H/sub 9/))Os/sub 3/(CO)/sub 10/ has been determined by X-ray crystallographic methods. The compound crystallizes in the centrosymmetric monoclinic space group P2/sub 1//n(C/sub 2h//sup 5/):a = 13.651 (4) A, b = 9.156 (4) A, c = 18.275 (5) A, ..beta.. = 111.42 (2)/sup 0/, V = 2126.3 (25) A/sup 3/, Z = 4, rho/sub calcd/ = 2.92 g cm/sup -3/. A uniform triangular cluster of three osmium atoms contains ten linear carbonyl groups and a ..mu..-eta/sup 1/-C==N(H)(t-C/sub 4/H/sub 9/) iminyl ligand. The carbon atom of the iminyl ligand symmetrically bridges one osmium-osmium bond, as is shown by the internuclear separations Os(2)-C(11) = 2.066 (8) A and Os(3)-C(11) = 2.043 (8) A. The iminyl bond, C(11)-N, is double with the C-N distance being 1.298 (10) A.

Reactions of small molecules with transition metal cluster hydrides. The reaction of H2Os3(CO)10 with aryl-isocyanates and -isothiocyanates

Abstract The transition metal cluster hydride complex H 2 Os 3 (CO) 10 reacts with aryl isocyanates and isothiocyanates to yield products containing N-aryl-formamido and -thioformamido ligands. The compound (μ-p-CH 3 C 6 H 4 NC(H)O) (μ-H)Os 3 (CO) 10 has been analyzed by x-ray crystallographic methods and is shown to contain a formamido ligand bridging the edge of the triosmium cluster.

Activation of small molecules by transition metal cluster compounds. Oxidative cleavage of a metal-metal bond by HCl in an osmium cluster compound

The complex (μ3-S)(μ3-n2-SCH2)Os3(CO)8[P(CH3)2C6H5] reacts with HCl in an addition process to form the molecule (μ3-S)(μ3-n2-SCH2)(H)Os3(CO)8[P(CH3)2C6H5]Cl. The product was characterized by IR, 1H NMR and x-ray crystallographic methods. The structural analysis shows that the HCl addition has caused a cleavage of one of the metal-metal bonds.