Higher Nuclearity Clusters Containing Osmium and Tin Atoms. Synthesis and Structure of [(OC)₃Os(SnMe₂)]₃, Os₄(SnMe₂)₄(CO)₁₄, and Os₄(μ₃-O)₂(SnMe₂)₄(CO)₁₄

Abstract

Pyrolysis of [(OC) 4 Os(SnMe 2 )] 2 (1) at 170 °C gave [(OC) 3 Os(SnMe 2 )] 3 (2) as the major product. The structure of 2 reveals a planar triangulated (raftlike) Os 3 Sn 3 unit (6 h crystallographic symmetry, with Os-Os ) 2.974(1) Å and Os-Sn ) 2.667(1) and 2.673(1) Å). UV irradiation of 1 in hexane provided the yellow, insoluble Os 4 (SnMe 2 ) 4 (CO) 14 (3). The structure of 3 shows an essentially planar Os 4 Sn 4 skeleton comprised of a central rhomboidal Os 2 Sn 2 unit with each Os atom part of two outer Os 2 Sn triangles. The Os-Sn bonds of the Os 2 Sn 2 unit at 2.760(1) and 2.780(1) Å are significantly longer than the corresponding bonds of the Os 2 Sn groups (2.678(1) and 2.727(1) Å); the Os-Os bonds in 3 are long at 3.0414(5) Å. From the treatment of 1 in solution with Me 3 NO, Os 4 (µ 3 -O) 2 (SnMe 2 ) 4 (CO) 14 (4) was isolated in low yield. The structure of 4 has a central six-membered (OsOSn) 2 ring to which are fused two OsOSnOs rings such that each outer ring shares a common OsO edge with the central ring. The outer rings of 4 are planar, but the central ring has a boat conformation.

Synthesis of new heterometallic complexes by tin–sulfur bond cleavage of pySSnPh3 (pySH = pyridine-2-thiol) at triruthenium and triosmium centres

“…The most widely used method is the oxidative-addition of organotin hydrides and using this methodology a number of transition metal-tin clusters with intriguing structural features have been synthesized, as exemplified by the work of Adams and co-workers [15][16][17][18][19][20][21][22][23][24][25][26]. More recently other tin-element oxidative-addition reactions have been exploited, for example Gárate-Morales and Fernández-G have prepared amine-containing osmium-tin compounds via the cleavage of the nitrogen-tin bond in aminostannanes [27][28][29].…”

Synthesis and Structure of [Os(CO)4(SnPh2)]6: A Compound with an Unprecedented 12-Membered Ring of Metal Atoms

“…It has been previously established for complexes of the type M(CO) 4 (ER 3- x Cl x ) 2 (M = Fe, Ru, Os; E = Si, Ge, Sn; R = organic group) that the trans isomer is favored for M = Os, ,, R = bulky group, , and x = 3 (i.e., for the electron-withdrawing ECl 3 ligands). ,, Furthermore, interconversion of the cis and trans forms of complexes such as Os(CO) 4 (SiMeCl 2 ) 2 is sufficiently slow that the two isomers may be separated at room temperature , Furthermore, we have found no evidence for the Ge, or Pb, analogue of 1 in the reaction of Ph 2 GeCl 2 , or Ph 2 PbCl 2 , with the osmium anion. It may be that the formation of the germanium derivative is prevented due to increased across-ring repulsions arising from the shorter Os−Ge bonds.…”

“…Compound 2 with a planar four-membered ring of metal atoms was the expected product. It has been found that reactions of [M(CO) 4 ] 2- (M = Fe, Ru, Os) with R 2 ECl 2 (E = Ge, Sn, Pb; R = Me, Bu t ) yield analogous derivatives with M 2 E 2 units. − The spectroscopic properties of 2 are unremarkable.

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“…The structural motifs exhibited by molecules with group 8 metals and the heavier 14 elements are many and diverse . Recent work from this laboratory has described the synthesis and structure of several Os−Ge and Os−Sn clusters with various skeletal geometries. , One of these, Os 4 (SnMe 2 ) 4 (CO) 14 , was envisaged as the result of dimerization of Os 2 (SnMe 2 ) 2 (CO) 7 , which in turn was the product of loss of CO from the precursor [Os(CO) 4 (SnMe 2 )] 2 …”

Raft-like osmium- and ruthenium-antimony carbonyl clusters

“…The metal cores in the latter group of clusters are rather distorted from planarity and have been referred to simply as "two-dimensional" clusters. Examples containing a main group metal or metalloid include several with Ge or Sn, obtained via the addition of germylene [5] or Ph 3 MH (M ¼ Ge or Sn) [6], to M 3 (CO) 12 (M ¼ Os or Ru), or via the pyrolysis of lownuclearity osmium [7], or ruthenium [8], clusters containing Ge ligands; these cluster tend to be planar.…”