An improved synthesis of Os6 raft-like clusters

Goudsmit, Robert J.; Jeffrey, John G.; Johnson, Brian F. G.; Lewis, Jack; McQueen, Roderick C. S.; Sanders, Arthur; Liu, Jia-Chu

doi:10.1039/c39860000024

Cited by 23 publications

(5 citation statements)

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“…E 1/2 = Ϫ0.36 and Ϫ0.20 V vs. Ag-AgNO 3 . It is likely that these couples are metal-based, generally in line with those obtained by Drake 18 and Goudsmit et al 19 for triangular hexaosmium raft systems. An additional irreversible anodic wave appearing at ca.…”

Section: Resultssupporting

confidence: 84%

Formation of hexaosmium raft clusters from [Os6(CO)16(MeCN)2]: synthesis, structural characterisation and reactivities of [Os6(CO)16(μ3-η2-C5H4NS)2] and [Os6(CO)17(μ-H)(μ4-η2-C5H4NS)]

Leung¹,

Wong²

1999

J. Chem. Soc., Dalton Trans.

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Section: Resultssupporting

confidence: 84%

Formation of hexaosmium raft clusters from [Os6(CO)16(MeCN)2]: synthesis, structural characterisation and reactivities of [Os6(CO)16(μ3-η2-C5H4NS)2] and [Os6(CO)17(μ-H)(μ4-η2-C5H4NS)]

Leung¹,

Wong²

1999

J. Chem. Soc., Dalton Trans.

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“…Given that GeMe 2 is isolobal with Os(CO) 4 , it is not surprising that some of the clusters described here have analogues among the binary carbonyls of osmium; thus, the analogues of 1 , 3 , and 4 are Os 4 (CO) 16 , Os 5 (CO) 19 , and Os 6 (CO) 21 , respectively. There is no binary carbonyl of osmium analogous to 5 .…”

Section: Resultsmentioning

confidence: 85%

Osmium−Germanium Clusters. Structures of [(OC)₄Os(GeMe₂)]₂, Os₂(GeMe₂)₃(CO)₆, Os₃(GeMe₂)₂(CO)₁₁, [(OC)₃Os(GeMe₂)]₃, and Os₄(GeMe₂)₄(CO)₁₂

1996

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The complex [(OC) 4 Os(GeMe 2 )] 2 (1) has been prepared from Na 2 [Os(CO) 4 ] and Me 2 GeCl 2 in THF. Photolysis of 1 in hexane affords the known [(OC) 3 Os(GeMe 2 )] 3 (4) as the major product, along with the new clusters Os 3 (GeMe 2 ) 2 (CO) 11 (3) and Os 4 (GeMe 2 ) 4 (CO) 12 (5). Pyrolysis of 1, in hexane at 100 °C, gives the same compounds except that Os 2 (GeMe 2 ) 3 -(CO) 6 (2) was also isolated, albeit in low yield. The structures of 1-5 have been determined; the configurations of 1, 2, and 4 are analogous to those previously found for group 8-group 14 congeners. The skeleton of 3 consists of two Os 2 Ge triangles that share a common osmium atom, that is, a "bow-tie" arrangement; the Os-Os lengths in 3 are crystallographically equivalent at 2.981(1) Å, and the Os-Ge lengths are 2.520(1) and 2.522(1) Å. The framework of 5 consists of a central triangulated (raftlike) Os 3 Ge 3 unit (similar to that in 4) to one Os atom of which is bound an (OC) 4 Os(GeMe 2 ) fragment so as to give an Os 2 Ge triangle that lies in the plane of the other metal atoms. The Os-Os bond length associated with this triangle is long (3.069(1) Å). The other Os-Os lengths in 4 range from 2.860(1) to 2.967(1) Å; the Os-Ge lengths are in the range 2.475(2)-2.584(2) Å. The 1 H NMR spectrum of 5 in toluene-d 8 is consistent with rotation of the (OC) 4 Os(GeMe 2 ) unit with respect to the rest of the molecule at temperatures above 60 °C.

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“…The structure of 1 may also be compared to those of Os 5 (μ-CO)(CO) 17 2b,c and Os 6 (CO) 17 [P(OMe) 3 ] 4 , which also have planar triangulated metal skeletons. The structure of Os 6 (CO) 21 , to which 2 is an isolobal analogue, has not been determined but presumably has an Os 6 raft nucleus …”

Section: Resultsmentioning

confidence: 99%

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

1996

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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.

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An improved synthesis of Os6 raft-like clusters

Abstract: The new, activated, raft clusters [ O S ~( C O ) ~~( M ~C N ) ] and [ O S ~( C O ) ~~( M ~C N ) ~] have been prepared by the coupling of

Cited by 23 publications

References 0 publications

Formation of hexaosmium raft clusters from [Os6(CO)16(MeCN)2]: synthesis, structural characterisation and reactivities of [Os6(CO)16(μ3-η2-C5H4NS)2] and [Os6(CO)17(μ-H)(μ4-η2-C5H4NS)]

Formation of hexaosmium raft clusters from [Os6(CO)16(MeCN)2]: synthesis, structural characterisation and reactivities of [Os6(CO)16(μ3-η2-C5H4NS)2] and [Os6(CO)17(μ-H)(μ4-η2-C5H4NS)]

Osmium−Germanium Clusters. Structures of [(OC)₄Os(GeMe₂)]₂, Os₂(GeMe₂)₃(CO)₆, Os₃(GeMe₂)₂(CO)₁₁, [(OC)₃Os(GeMe₂)]₃, and Os₄(GeMe₂)₄(CO)₁₂

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

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An improved synthesis of Os6 raft-like clusters

Abstract: The new, activated, raft clusters [ O S ~( C O ) ~~( M ~C N ) ] and [ O S ~( C O ) ~~( M ~C N ) ~] have been prepared by the coupling of

Cited by 23 publications

References 0 publications

Formation of hexaosmium raft clusters from [Os6(CO)16(MeCN)2]: synthesis, structural characterisation and reactivities of [Os6(CO)16(μ3-η2-C5H4NS)2] and [Os6(CO)17(μ-H)(μ4-η2-C5H4NS)]

Formation of hexaosmium raft clusters from [Os6(CO)16(MeCN)2]: synthesis, structural characterisation and reactivities of [Os6(CO)16(μ3-η2-C5H4NS)2] and [Os6(CO)17(μ-H)(μ4-η2-C5H4NS)]

Osmium−Germanium Clusters. Structures of [(OC)4Os(GeMe2)]2, Os2(GeMe2)3(CO)6, Os3(GeMe2)2(CO)11, [(OC)3Os(GeMe2)]3, and Os4(GeMe2)4(CO)12

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

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Osmium−Germanium Clusters. Structures of [(OC)₄Os(GeMe₂)]₂, Os₂(GeMe₂)₃(CO)₆, Os₃(GeMe₂)₂(CO)₁₁, [(OC)₃Os(GeMe₂)]₃, and Os₄(GeMe₂)₄(CO)₁₂

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