Tetrakis(μ-triisopropylsilanethiolato)-1:2κ⁴S:S;2:3κ⁴S:S-bis(triisopropylsilanethiolato)-1κS,3κS-trizinc(II)

Abstract

The title compound, [Zn(3)(C(9)H(21)SiS)(6)] or [((i)Pr(3)SiS)Zn(mu-SSi(i)Pr(3))(2)Zn(mu-SSi(i)Pr(3))(2)Zn(SSi(i)Pr(3))], is the first structurally characterized homoleptic silanethiolate complex of zinc. A near-linear arrangement of three Zn(II) ions is observed, the metals at the ends being three-coordinate with one terminally bound silanethiolate ligand. The central Zn(II) ion is four-coordinate and tetrahedral, with two bridging silanethiolate ligands joining it to each of the two peripheral Zn(II) ions. The nonbonding intermetallic distances are 3.1344 (11) and 3.2288 (12) A, while the Zn...Zn...Zn angle is 172.34 (2) degrees. A trimetallic silanethiolate species of this type has not been previously identified by X-ray crystallography for any element.

Synthesis and characterization of mononuclear Zn(ii), Co(ii) and Ni(ii) complexes containing a sterically demanding silanethiolate ligand derived from tris(2,6-diisopropylphenoxy)silanethiol

“…17 The structural studies confirmed that as a result of the syntheses we have obtained heteroleptic silanethiolate com-plexes of nickel(II), cobalt(II), and zinc(II). It is certainly possible to obtain homoleptic chalkogenolates of these metals; such as Zn, Ni, Co alkyl-and arenethiolates, 12,[18][19][20][21] Zn silanethiolates 22 and also one Zn silanetelluroate 23 were described. Among various aggregation patterns small M 2 S 2 rings are often found [18][19][20]22,23 as well as ubiquitous clusters of higher nuclearity.…”

“…It is certainly possible to obtain homoleptic chalkogenolates of these metals; such as Zn, Ni, Co alkyl-and arenethiolates, 12,[18][19][20][21] Zn silanethiolates 22 and also one Zn silanetelluroate 23 were described. Among various aggregation patterns small M 2 S 2 rings are often found [18][19][20]22,23 as well as ubiquitous clusters of higher nuclearity. 18,21,22 Homoleptic tri-tert-butoxysilanethiolate complexes of cadmium and mercury were obtained and characterized by Wojnowski and co-workers.…”

“…Among various aggregation patterns small M 2 S 2 rings are often found [18][19][20]22,23 as well as ubiquitous clusters of higher nuclearity. 18,21,22 Homoleptic tri-tert-butoxysilanethiolate complexes of cadmium and mercury were obtained and characterized by Wojnowski and co-workers. 24,25 The crystal structure of binuclear cadmium tri-tert-butoxysilanethiolate features a M 2 S 2 ring.…”

Intramolecular Interactions in Crystals of Tris(2,6-diisopropylphenoxy)silanethiol and Its Sodium Salts

“…Silanethiolate complexes with less sterical hindrance about the silicon atom were usually reported as the potential precursors to metal–sulfur clusters and particles. These included trimethylsilanethiolates, triisopropylsilanethiolate, and triphenylsilanethiolates. , Mixed-ligand silanethiolate cadmium complexes were probed as precursors of CdS thin films …”