Selection of the cis and trans phosph(III)azane macrocycles [{P(μ-N tBu)}2(1-Y-2-NH-C6H4)]2 (Y = O, S)

Felipe García; Jonathan M. Goodman; Richard A. Kowenicki; Mary McPartlin; Lucía Riera; Maria A. Silva; Andreas Wirsing; Dominic S. Wright

doi:10.1039/b502200b

Selection of the cis and trans phosph(III)azane macrocycles [{P(μ-N ^tBu)}₂(1-Y-2-NH-C₆H₄)]₂ (Y = O, S)

Felipe García, Jonathan M. Goodman, Richard A. Kowenicki, Mary McPartlin, Lucía Riera, Maria A. Silva, Andreas Wirsing, Dominic S. Wright

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

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Abstract

The 1:1 reactions of [ClP(μ-N^tBu)]₂ with the difunctional aromatic amines 1,2-1-YH-2-NH₂-C₆H ₄ in the presence of Et₃N give the dimeric phosph(III)azane macrocycles [{P(μ-N_tBu)₂(1-Y-2-HN- C₆H₄)]², predominantly as the cis isomer in the case of Y = O (1·cis) and as the trans isomer for Y = S (2·trans). Model M.O. calculations suggest that the selection of the cis and Irans isomers is not thermodynamically controlled. The alternative isomers 1·trans and 2·cis are generated exclusively by the deprotonation of the model intermediates [(1-Y-2-NH₂-C₆H ₄)P(μ-N^tBu)]₂ [Y = O (3), S (4)] with ″BuLi followed by cyclisation with [ClP(μ-N^tBu)] ₂. The solid-state structures of 1·cis/trans (50:50), 2·cis, 3 and 4 are reported.

Original language	English
Pages (from-to)	1764-1773
Number of pages	10
Journal	Dalton Transactions
Issue number	10
DOIs	https://doi.org/10.1039/b502200b
Publication status	Published - 21 May 2005
Externally published	Yes

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title = "Selection of the cis and trans phosph(III)azane macrocycles [{P(μ-N tBu)}2(1-Y-2-NH-C6H4)]2 (Y = O, S)",

abstract = "The 1:1 reactions of [ClP(μ-NtBu)]2 with the difunctional aromatic amines 1,2-1-YH-2-NH2-C6H 4 in the presence of Et3N give the dimeric phosph(III)azane macrocycles [{P(μ-NtBu)2(1-Y-2-HN- C6H4)]2, predominantly as the cis isomer in the case of Y = O (1·cis) and as the trans isomer for Y = S (2·trans). Model M.O. calculations suggest that the selection of the cis and Irans isomers is not thermodynamically controlled. The alternative isomers 1·trans and 2·cis are generated exclusively by the deprotonation of the model intermediates [(1-Y-2-NH2-C6H 4)P(μ-NtBu)]2 [Y = O (3), S (4)] with ″BuLi followed by cyclisation with [ClP(μ-NtBu)] 2. The solid-state structures of 1·cis/trans (50:50), 2·cis, 3 and 4 are reported.",

author = "Felipe Garc{\'i}a and Goodman, {Jonathan M.} and Kowenicki, {Richard A.} and Mary McPartlin and Luc{\'i}a Riera and Silva, {Maria A.} and Andreas Wirsing and Wright, {Dominic S.}",

year = "2005",

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doi = "10.1039/b502200b",

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T1 - Selection of the cis and trans phosph(III)azane macrocycles [{P(μ-N tBu)}2(1-Y-2-NH-C6H4)]2 (Y = O, S)

AU - García, Felipe

AU - Goodman, Jonathan M.

AU - Kowenicki, Richard A.

AU - McPartlin, Mary

AU - Riera, Lucía

AU - Silva, Maria A.

AU - Wirsing, Andreas

AU - Wright, Dominic S.

PY - 2005/5/21

Y1 - 2005/5/21

N2 - The 1:1 reactions of [ClP(μ-NtBu)]2 with the difunctional aromatic amines 1,2-1-YH-2-NH2-C6H 4 in the presence of Et3N give the dimeric phosph(III)azane macrocycles [{P(μ-NtBu)2(1-Y-2-HN- C6H4)]2, predominantly as the cis isomer in the case of Y = O (1·cis) and as the trans isomer for Y = S (2·trans). Model M.O. calculations suggest that the selection of the cis and Irans isomers is not thermodynamically controlled. The alternative isomers 1·trans and 2·cis are generated exclusively by the deprotonation of the model intermediates [(1-Y-2-NH2-C6H 4)P(μ-NtBu)]2 [Y = O (3), S (4)] with ″BuLi followed by cyclisation with [ClP(μ-NtBu)] 2. The solid-state structures of 1·cis/trans (50:50), 2·cis, 3 and 4 are reported.

AB - The 1:1 reactions of [ClP(μ-NtBu)]2 with the difunctional aromatic amines 1,2-1-YH-2-NH2-C6H 4 in the presence of Et3N give the dimeric phosph(III)azane macrocycles [{P(μ-NtBu)2(1-Y-2-HN- C6H4)]2, predominantly as the cis isomer in the case of Y = O (1·cis) and as the trans isomer for Y = S (2·trans). Model M.O. calculations suggest that the selection of the cis and Irans isomers is not thermodynamically controlled. The alternative isomers 1·trans and 2·cis are generated exclusively by the deprotonation of the model intermediates [(1-Y-2-NH2-C6H 4)P(μ-NtBu)]2 [Y = O (3), S (4)] with ″BuLi followed by cyclisation with [ClP(μ-NtBu)] 2. The solid-state structures of 1·cis/trans (50:50), 2·cis, 3 and 4 are reported.

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DO - 10.1039/b502200b

M3 - Article

C2 - 15877146

AN - SCOPUS:19544373826

SN - 1477-9226

SP - 1764

EP - 1773

JO - Dalton Transactions

JF - Dalton Transactions

IS - 10

ER -

Selection of the cis and trans phosph(III)azane macrocycles [{P(μ-N tBu)}2(1-Y-2-NH-C6H4)]2 (Y = O, S)

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Selection of the cis and trans phosph(III)azane macrocycles [{P(μ-N ^tBu)}₂(1-Y-2-NH-C₆H₄)]₂ (Y = O, S)