Oligo(alkynylsilanes):  Templates for Organometallic Polymers

Abstract

A series of compounds containing alkynylsilane and arylsilane groups, including oligomers and polymers, were used as transition-metal ligands. The alkyne groups could be complexed by dicobalt hexacarbonyl. Alternatively, complexation of the aryl groups by chromium tricarbonyl readily took place. The molecular weights of these complexes ranged up to 155 000 for a silicone polymer derived complex. Mixed-metal clusters containing Cr/Mo and Cr/Co could be made by modifying the chromium derivatives with Mo2Cp2(CO)6 and Co2(CO)8, respectively. The model compound 20 shows an interesting self-assembly of the metals (Co and Cr, respectively) in the crystal.

Using Hydrosilylation To Assemble Organometallic Polymers Containing Combinations of Silicon-Based Functional Groups

“…This has been efficiently accomplished by using an iterative procedure. In an accompanying paper, 12 we describe the coordination of single and mixed organotransition-metal fragments to the ligands described in this paper. We further show an example in which a transition metal cluster was incorporated along the chain of a relatively high molecular weight siloxane polymer.…”

“…Furthermore, silicones are not affected to a great extent by neutral transition metal complexes, except that Si−H species can yield oxidative addition products . Consequently, we decided to use silicones as the matrix within which to interchangeably place selected combinations of sila-functional species with the goal of preparing polymers with potentially interesting optical and electronic properties …”

“…Mass spectrum (DEI, m/z (%)): 576 (8, [M] + ), 379 (100, [M s Me3-SiCtCSiMe 2CH2CH2CH2] + ), 73 (15,[Si(CH3)3] + ). Mass spectrum (high resolution, (DEI)): calcd for mass 12 C31H49Si5 ([M s CH 3] + ), 561.2681 amu; found, 561.2684 amu. Anal.…”

Hybrid metal–polymer composites from functional block copolymers

“…91,94,95 As initial copolymer species, we are examining ABC triblock copolymers containing alkyne-functional groups in one block, for the specific covalent attachment of metal complexes, along with the PVP blocks used in many of the studies described previously for metal coordination. 96 The connection of these two blocks with a nonfunctional center (B) block such as PS should allow the formation of a self-assembled polymer architecture, which might then enable the incorporation of two different metal species and facilitate, for example, the discrete inclusion of gold (complexed with the PVP block as the pyridinium tetrachloroaurate salt) and cobalt species (linked to the alkyne-functional block as the dicobalt hexacarbonyl complex) 97,98 within separate ordered nanometer-scale domains of the bulk block copolymer (Fig. 2).…”

Organometallic Polymers of the Transition Metals

“…[345] Reaction of the hexacarbonyldicobalt complex with the high-molecular-weight silicon-based polymer is shown in Scheme 80.…”