Crystal structure of hexakis(dimethyl-μ-oxosilane)dibromozirconium(IV) bis(nonabromodizirconate(IV)), [Zr{(CH3)2SiO}6Br2][Zr2Br9]2

Abstract

Source of materialThe compound wasprepared asabyproductfrom the bromination of Zr(C 5 H 5 ) 2 Br 2 in the presence of silicone grease [1,2], which in other cases canleadto[(CH 3 ) 2 SiO] 7 [3,4] and other related ligand systems [ 5]. Single crystals were formed directly from the unstirred reaction mixture over aperiod of two days. DiscussionThe titlecompound exists asasalt,with the dication possessing crystallographically imposed inversion symmetry, and being comprised of a trans-ZrBr 2 unit with equatorialcoordination arising from the oxygen atoms of a[Me 2 SiO] 6 ring. The Zr-Brdistance for the dication is 2.5338(6) Å,w hile four short and two long Zr-Odistances are observed, averaging 2.258(3) Åfor O1, O2, and 2.577(6) Åfor O3. The O1-Zr1-O2angle is 63.52 (1)

Solvothermal Alcoholysis Method for Recycling High-Consistency Silicone Rubber Waste

“…Silicone grease is generally considered to be chemically inert and is frequently used to seal ground-glass joints in Schlenk techniques. However, there are a number of examples in the literature of metal-bonded siloxane derivatives, i.e., {OSiMe 2 Cl} − , {O 2 SiMe 2 } 2– , − {OSiMe 2 OR} − , {(OSiMe 2 ) x O} 2– ( x = 2, − 3), and sila-crown ethers (Me 2 SiO) x ( x = 6 or 7), , which were formed when silicone grease was used during synthetic procedures. Most of these compounds were formed in a haphazard way when various metal derivatives (i.e., metal alkoxides and metal halides) or organometallic reagents (i.e., metal alkyls or metallocenes) were exposed to contact with silicone grease.…”

Modern concepts and methods in the chemistry of polyhedral metallasiloxanes

“…33) [140]. Perfectly planar molecules with Zr (96, [141]) and Ag (97 [142]) cations in the center of dimethylsiloxane cycles were reported subsequently (Fig. 34).…”

“…We suggest that these crown ether-like structures should be considered as a new class of metal-containing organosilicon compounds. 96 [141] 97 [142] Fig. 34.…”

Siloxane Coordination Revisited: Si−O Bond Character, Reactivity and Magnificent Molecular Shapes

“…Two more examples have been published in the meantime in which silicon grease has (unintentionally) been used as a precursor for the formation of D n complexes. An additional potassium compound in the form of the silyl‐sodate [K(D 7 )][Na{SiMe(Si t Bu 3 ) 2 } 2 ] [124] ( 3 ) was published by the group of Lerner and the zirconium(IV) complex [Zr(D 6 )Br 2 ][Zr 2 Br 9 ] 2 [125] ( 4 ) was published by Ernst . Parts of these structures are depicted in Figure 12.…”

“… The cationic structures of D n complexes obtained from serendipitous reactions with a silicon grease in crystal form. Depicted on the left is the cation [K(D 7 )] + of K 3 [K(D 7 )][InH(CH 2 CMe 3 ) 3 ] 4 [122] and depicted on the right is the cation [Zr(D 6 )Br 2 ] 2+ of [Zr(D 6 )Br 2 ][Zr 2 Br 9 ] 2 [125] . Atoms are displayed isotropically and with arbitrarily atom radii for clarity.…”