Acetylides transition metal

Transition Metal Acetylides for Nonlinear Optical Properties... 

Transition metal acetylides combine the properties of acetylenes with those of the transition metals, offering flexibility in the tuning of structural and electronic properties of both the organic and inorganic constituents. Optimization of the molecular and bulk crystalline properties is envisaged to lead to a new class of useful nonlinear optical materials. 

Electrical properties, rigid-rod transition metal—acetylide polymers, 12, 376... 

Hiickel band calculations, rigid-rod transition metal-acetylide polymers, 12, 371-372 Human health, tin toxic effects, 12, 637 Hybrid magnets, metallocene-containing bimetallic M(II)—Cr(II) oxalates, 12, 427 bimetallic M(II)-Fe(III) oxalates, 12, 432 bimetallic M(III)-Ru(III) oxalates, 12, 435 materials, 12, 437 properties, 12, 425 trimetallic oxalates, 12, 436 Hydantoins, with lead reagents, 3, 888 Hydration... 

Metal activation, and sonochemistry, 1, 314 Metal alkoxides, synthesis, 12, 51 Metal-to-alkyne ligand charge-transfer transitions, rigid-rod transition metal—acetylide polymers,... 

Although the reaction of copper acetylides with transition metal halides has been successfully applied to the preparation of a variety of transition metal acetylides (64), the generation of copper-complexed derivatives is not unprecedented (65). A simpler and more general route to ruthenium acetylide complexes involves the deprotonation of ruthenium vinylidene complexes as described in Section VI,C. 

The authors have previously reported33 a new convenient method of preparing transition metal-acetylide complexes of the type cis- and frans-(PR3)2M(C=CR)2 according to Eq. 10, and have shown that the complex having tri-n-butylphosphine as the ligand is air-stable and highly soluble in a variety of organic solvents. This new M-C bond formation reaction... 

Two poly(cyclodiborazane) polymers containing group-10 transition metal-acetylide groups P50 and P51 were prepared by Chujo et al. and represent a new kind of organometal-lic acetylide polymers functionalized with group-13 boron elements in the main chain.78 The structures of P50 and P51 were confirmed by IR and NMR ( H, 31P, and nB) spectra. The optical properties were studied by UV-vis absorption and emission measurements. It was shown that these polymers display extended -conjugation length via transition metal and boron atom with enhanced air- and moisture stability. 

An array of versatile and efficient step-growth polycondensation methodologies has been developed for the synthesis of transition metal-acetylide polymers. In this section, a representative review of the types of routes available and materials accessible is given. 

Transition-metal acetylides react readily with metal carbonyls to form derivatives. Thus (7t-Cp)2Ti(C CPh)2 and Ni(CO)4 afford (22). The oxidative additions of alkyl and acyl halides, RCOCl (R = Me or Ph), to [(7i-Cp)2Ti(CO)2] yield the corresponding [(7i-Cp)2Ti(Cl)C(0)R] compounds, and 9,10-phenanthraquinone affords (23). [(7i-Cp)2TiPh2] and [(7t-Cp)2 Ti(Me)Cl] have been shown to be active hydrogenation catalysts and the n.m.r. spectra of several [(7t-Cp)2TiR2] and [(7i-Cp)2Ti(R)Cl] compounds have been re-investigated and previous interpretations of such data questioned. ... 

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