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

Weng Kee Leong; Frederick W.B. Einstein; Roland K. Pomeroy

doi:10.1021/om950682c

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

Weng Kee Leong, Frederick W.B. Einstein, Roland K. Pomeroy^*

^*Corresponding author for this work

Simon Fraser University

Research output: Contribution to journal › Article › peer-review

19 Citations (Scopus)

Abstract

The complex [(OC)₄Os(GeMe₂)]₂ (1) has been prepared from Na₂[Os(CO)₄] and Me₂GeCl₂ in THF. Photolysis of 1 in hexane affords the known [(OC)₃Os(GeMe₂)]₃ (4) as the major product, along with the new clusters Os₃(GeMe₂)₂(CO)₁₁ (3) and Os₄(GeMe₂)₄(CO)₁₂ (5). Pyrolysis of 1, in hexane at 100 °C, gives the same compounds except that Os₂(GeMe₂)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 Os₂Ge 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) A, and the Os-Ge lengths are 2.520(1) and 2.522(1) Å. The framework of 5 consists of a central triangulated (raftlike) Os₃Ge₃ unit (similar to that in 4) to one Os atom of which is bound an (OC)₄Os(GeMe₂) fragment so as to give an Os₂Ge 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 ¹H NMR spectrum of 5 in toluene-d₈ is consistent with rotation of the (OC)₄Os(GeMe₂) unit with respect to the rest of the molecule at temperatures above 60 °C.

Original language	English
Pages (from-to)	1589-1596
Number of pages	8
Journal	Organometallics
Volume	15
Issue number	6
DOIs	https://doi.org/10.1021/om950682c
Publication status	Published - Mar 19 1996
Externally published	Yes

ASJC Scopus Subject Areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{fe22be02148848909cf1432bd1353884,

title = "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",

abstract = "The complex [(OC)4Os(GeMe2)]2 (1) has been prepared from Na2[Os(CO)4] and Me2GeCl2 in THF. Photolysis of 1 in hexane affords the known [(OC)3Os(GeMe2)]3 (4) as the major product, along with the new clusters Os3(GeMe2)2(CO)11 (3) and Os4(GeMe2)4(CO)12 (5). Pyrolysis of 1, in hexane at 100 °C, gives the same compounds except that Os2(GeMe2)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 Os2Ge 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) A, and the Os-Ge lengths are 2.520(1) and 2.522(1) {\AA}. The framework of 5 consists of a central triangulated (raftlike) Os3Ge3 unit (similar to that in 4) to one Os atom of which is bound an (OC)4Os(GeMe2) fragment so as to give an Os2Ge 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) {\AA}). The other Os-Os lengths in 4 range from 2.860(1) to 2.967(1) {\AA}; the Os-Ge lengths are in the range 2.475(2)-2.584(2) {\AA}. The 1H NMR spectrum of 5 in toluene-d8 is consistent with rotation of the (OC)4Os(GeMe2) unit with respect to the rest of the molecule at temperatures above 60 °C.",

author = "Leong, {Weng Kee} and Einstein, {Frederick W.B.} and Pomeroy, {Roland K.}",

year = "1996",

month = mar,

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doi = "10.1021/om950682c",

language = "English",

volume = "15",

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journal = "Organometallics",

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publisher = "American Chemical Society",

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T1 - 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

AU - Leong, Weng Kee

AU - Einstein, Frederick W.B.

AU - Pomeroy, Roland K.

PY - 1996/3/19

Y1 - 1996/3/19

N2 - The complex [(OC)4Os(GeMe2)]2 (1) has been prepared from Na2[Os(CO)4] and Me2GeCl2 in THF. Photolysis of 1 in hexane affords the known [(OC)3Os(GeMe2)]3 (4) as the major product, along with the new clusters Os3(GeMe2)2(CO)11 (3) and Os4(GeMe2)4(CO)12 (5). Pyrolysis of 1, in hexane at 100 °C, gives the same compounds except that Os2(GeMe2)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 Os2Ge 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) A, and the Os-Ge lengths are 2.520(1) and 2.522(1) Å. The framework of 5 consists of a central triangulated (raftlike) Os3Ge3 unit (similar to that in 4) to one Os atom of which is bound an (OC)4Os(GeMe2) fragment so as to give an Os2Ge 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 1H NMR spectrum of 5 in toluene-d8 is consistent with rotation of the (OC)4Os(GeMe2) unit with respect to the rest of the molecule at temperatures above 60 °C.

AB - The complex [(OC)4Os(GeMe2)]2 (1) has been prepared from Na2[Os(CO)4] and Me2GeCl2 in THF. Photolysis of 1 in hexane affords the known [(OC)3Os(GeMe2)]3 (4) as the major product, along with the new clusters Os3(GeMe2)2(CO)11 (3) and Os4(GeMe2)4(CO)12 (5). Pyrolysis of 1, in hexane at 100 °C, gives the same compounds except that Os2(GeMe2)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 Os2Ge 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) A, and the Os-Ge lengths are 2.520(1) and 2.522(1) Å. The framework of 5 consists of a central triangulated (raftlike) Os3Ge3 unit (similar to that in 4) to one Os atom of which is bound an (OC)4Os(GeMe2) fragment so as to give an Os2Ge 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 1H NMR spectrum of 5 in toluene-d8 is consistent with rotation of the (OC)4Os(GeMe2) unit with respect to the rest of the molecule at temperatures above 60 °C.

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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

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