Stepwise conversion of an osmium trimethylstannyl complex to a triiodostannyl complex and nucleophilic substitution reactions at the tin-iodine bonds

Alex M. Clark; Clifton E.F. Rickard; Warren R. Roper; Timothy J. Woodman; L. James Wright

doi:10.1021/om990904x

Stepwise conversion of an osmium trimethylstannyl complex to a triiodostannyl complex and nucleophilic substitution reactions at the tin-iodine bonds

Alex M. Clark, Clifton E.F. Rickard, Warren R. Roper, Timothy J. Woodman, L. James Wright

Auckland University of Technology

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

35 Citations (SciVal)

Abstract

Treatment of the coordinatively unsaturated osmium complex Os(SnMe₃)Cl(CO)(PPh₃)₂ with sodium dimethyldithiocarbamate gives the coordinatively saturated complex Os(SnMe₃)(η²-S₂CNMe₂)(CO)(PPh₃)₂ (1). Complex 1 reacts with excess SnI₄ to give Os(SnMeI₂)(η²-S₂CNMe₂)(CO)(PPh₃)₂ (3) in high yield. A redistribution reaction of 3 with an equimolar amount of 1 provides Os(SnMe₂I)(η²-S₂CNMe₂)(CO)(PPh₃)₂ (2). The last remaining methyl group bonded to tin in 3 is removed by treatment with a slight excess of I₂, giving the triiodostannyl complex Os(SnI₃)(η²-S₂CNMe₂)(CO)(PPh₃)₂ (4). Both 3 and 4 have been further derivatized by replacement of the halide groups on tin. Treatment of 3 with pyridinium tribromide gives Os(SnMeBr₂)(η²-S₂CNMe₂)(CO)(PPh₃)₂ (5). Treatment of 3 with catechol provides Os(SnMe[1,2-O₂C₆H₄]) (η²-S₂CNMe₂)(CO)(PPh₃)₂ (6), while the similar reaction with 1,2-ethanedithiol gives Os(SnMe[1,2-S₂C₂H₄]) (η²-S₂CNMe₂)(CO)(PPh₃)₂ (7). Complex 4 undergoes reaction with an excess of KOH to give the trihydroxystannyl complex Os(Sn[OH]₃)(η²-S₂CNMe₂)(CO)(PPh₃)₂ (8). Treatment of 4 with triethanolamine gives Os(Sn[OCH₂CH₂]₃N) (η²-S₂CNMe₂)(CO)(PPh₃)₂ (9), while reaction with nitrilotriacetic acid gives the metal-substituted stannatranone Os(Sn[OC(O)CH₂]₃N)(η²-S₂CNMe₂)(CO) (PPh₃)₂ (10). The crystal structures of 1, 4, 5, 7, and 10 have been determined.

Original language	English
Pages (from-to)	1766-1774
Number of pages	9
Journal	Organometallics
Volume	19
Issue number	9
DOIs	https://doi.org/10.1021/om990904x
Publication status	Published - 1 May 2000

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/om990904x

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@article{0b0aef99fbae466f961a7d441a632650,

title = "Stepwise conversion of an osmium trimethylstannyl complex to a triiodostannyl complex and nucleophilic substitution reactions at the tin-iodine bonds",

abstract = "Treatment of the coordinatively unsaturated osmium complex Os(SnMe3)Cl(CO)(PPh3)2 with sodium dimethyldithiocarbamate gives the coordinatively saturated complex Os(SnMe3)(η2-S2CNMe2)(CO)(PPh3)2 (1). Complex 1 reacts with excess SnI4 to give Os(SnMeI2)(η2-S2CNMe2)(CO)(PPh3)2 (3) in high yield. A redistribution reaction of 3 with an equimolar amount of 1 provides Os(SnMe2I)(η2-S2CNMe2)(CO)(PPh3)2 (2). The last remaining methyl group bonded to tin in 3 is removed by treatment with a slight excess of I2, giving the triiodostannyl complex Os(SnI3)(η2-S2CNMe2)(CO)(PPh3)2 (4). Both 3 and 4 have been further derivatized by replacement of the halide groups on tin. Treatment of 3 with pyridinium tribromide gives Os(SnMeBr2)(η2-S2CNMe2)(CO)(PPh3)2 (5). Treatment of 3 with catechol provides Os(SnMe[1,2-O2C6H4]) (η2-S2CNMe2)(CO)(PPh3)2 (6), while the similar reaction with 1,2-ethanedithiol gives Os(SnMe[1,2-S2C2H4]) (η2-S2CNMe2)(CO)(PPh3)2 (7). Complex 4 undergoes reaction with an excess of KOH to give the trihydroxystannyl complex Os(Sn[OH]3)(η2-S2CNMe2)(CO)(PPh3)2 (8). Treatment of 4 with triethanolamine gives Os(Sn[OCH2CH2]3N) (η2-S2CNMe2)(CO)(PPh3)2 (9), while reaction with nitrilotriacetic acid gives the metal-substituted stannatranone Os(Sn[OC(O)CH2]3N)(η2-S2CNMe2)(CO) (PPh3)2 (10). The crystal structures of 1, 4, 5, 7, and 10 have been determined.",

author = "Clark, {Alex M.} and Rickard, {Clifton E.F.} and Roper, {Warren R.} and Woodman, {Timothy J.} and Wright, {L. James}",

year = "2000",

month = may,

day = "1",

doi = "10.1021/om990904x",

language = "English",

volume = "19",

pages = "1766--1774",

journal = "Organometallics",

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publisher = "American Chemical Society",

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T1 - Stepwise conversion of an osmium trimethylstannyl complex to a triiodostannyl complex and nucleophilic substitution reactions at the tin-iodine bonds

AU - Clark, Alex M.

AU - Rickard, Clifton E.F.

AU - Roper, Warren R.

AU - Woodman, Timothy J.

AU - Wright, L. James

PY - 2000/5/1

Y1 - 2000/5/1

N2 - Treatment of the coordinatively unsaturated osmium complex Os(SnMe3)Cl(CO)(PPh3)2 with sodium dimethyldithiocarbamate gives the coordinatively saturated complex Os(SnMe3)(η2-S2CNMe2)(CO)(PPh3)2 (1). Complex 1 reacts with excess SnI4 to give Os(SnMeI2)(η2-S2CNMe2)(CO)(PPh3)2 (3) in high yield. A redistribution reaction of 3 with an equimolar amount of 1 provides Os(SnMe2I)(η2-S2CNMe2)(CO)(PPh3)2 (2). The last remaining methyl group bonded to tin in 3 is removed by treatment with a slight excess of I2, giving the triiodostannyl complex Os(SnI3)(η2-S2CNMe2)(CO)(PPh3)2 (4). Both 3 and 4 have been further derivatized by replacement of the halide groups on tin. Treatment of 3 with pyridinium tribromide gives Os(SnMeBr2)(η2-S2CNMe2)(CO)(PPh3)2 (5). Treatment of 3 with catechol provides Os(SnMe[1,2-O2C6H4]) (η2-S2CNMe2)(CO)(PPh3)2 (6), while the similar reaction with 1,2-ethanedithiol gives Os(SnMe[1,2-S2C2H4]) (η2-S2CNMe2)(CO)(PPh3)2 (7). Complex 4 undergoes reaction with an excess of KOH to give the trihydroxystannyl complex Os(Sn[OH]3)(η2-S2CNMe2)(CO)(PPh3)2 (8). Treatment of 4 with triethanolamine gives Os(Sn[OCH2CH2]3N) (η2-S2CNMe2)(CO)(PPh3)2 (9), while reaction with nitrilotriacetic acid gives the metal-substituted stannatranone Os(Sn[OC(O)CH2]3N)(η2-S2CNMe2)(CO) (PPh3)2 (10). The crystal structures of 1, 4, 5, 7, and 10 have been determined.

AB - Treatment of the coordinatively unsaturated osmium complex Os(SnMe3)Cl(CO)(PPh3)2 with sodium dimethyldithiocarbamate gives the coordinatively saturated complex Os(SnMe3)(η2-S2CNMe2)(CO)(PPh3)2 (1). Complex 1 reacts with excess SnI4 to give Os(SnMeI2)(η2-S2CNMe2)(CO)(PPh3)2 (3) in high yield. A redistribution reaction of 3 with an equimolar amount of 1 provides Os(SnMe2I)(η2-S2CNMe2)(CO)(PPh3)2 (2). The last remaining methyl group bonded to tin in 3 is removed by treatment with a slight excess of I2, giving the triiodostannyl complex Os(SnI3)(η2-S2CNMe2)(CO)(PPh3)2 (4). Both 3 and 4 have been further derivatized by replacement of the halide groups on tin. Treatment of 3 with pyridinium tribromide gives Os(SnMeBr2)(η2-S2CNMe2)(CO)(PPh3)2 (5). Treatment of 3 with catechol provides Os(SnMe[1,2-O2C6H4]) (η2-S2CNMe2)(CO)(PPh3)2 (6), while the similar reaction with 1,2-ethanedithiol gives Os(SnMe[1,2-S2C2H4]) (η2-S2CNMe2)(CO)(PPh3)2 (7). Complex 4 undergoes reaction with an excess of KOH to give the trihydroxystannyl complex Os(Sn[OH]3)(η2-S2CNMe2)(CO)(PPh3)2 (8). Treatment of 4 with triethanolamine gives Os(Sn[OCH2CH2]3N) (η2-S2CNMe2)(CO)(PPh3)2 (9), while reaction with nitrilotriacetic acid gives the metal-substituted stannatranone Os(Sn[OC(O)CH2]3N)(η2-S2CNMe2)(CO) (PPh3)2 (10). The crystal structures of 1, 4, 5, 7, and 10 have been determined.

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ER -

Stepwise conversion of an osmium trimethylstannyl complex to a triiodostannyl complex and nucleophilic substitution reactions at the tin-iodine bonds

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