Chiral bisphosphinite metalloligands derived from a P-chiral secondary phosphine oxide

Eddie Y.Y. Chan; Qian Feng Zhang; Yiu Keung Sau; Samuel M.F. Lo; Herman H.Y. Sung; Ian D. Williams; Richard K. Haynes; Wa Hung Leung

doi:10.1021/ic049744u

Chiral bisphosphinite metalloligands derived from a P-chiral secondary phosphine oxide

Eddie Y.Y. Chan, Qian Feng Zhang, Yiu Keung Sau, Samuel M.F. Lo, Herman H.Y. Sung, Ian D. Williams, Richard K. Haynes, Wa Hung Leung

Hong Kong University of Science and Technology

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

36 Citations (Scopus)

Abstract

Interaction of PdCl₂(MeCN)₂ with 2 equiv of (S _p)-^tBuPhP(O)H (1H) followed by treatment with Et ₃N gave [Pd-{(1)₂H}]₂(μ-Cl)₂ (2). Reaction of 2 with Na[S₂CNEt₂] or K[N(PPh ₂S)₂] afforded Pd[(1)₂H](S₂CNEt ₂) (3) or Pd[(1)₂H)-[N(PPh₂S)₂] (4), respectively. Treatment of 3 with V(O)(acac)₂ (acac = acetylacetonate) and CuSO₄ in the presence of Et₃N afforded bimetallic complexes V(O)[Pd(1)₂(S₂CNEt ₂)]₂ (5) or Cu[Pd(1)₂(S₂CNEt ₂)]₂ (6), respectively. X-ray crystallography established the S_p configuration for the phosphinous acid ligands in 3 and 6, indicating that 1H binds to Pd(II) with retention of configuration at phosphorus. The geometry around Cu in 6 is approximately square planar with the average Cu-O distance of 1.915(3) Å. Treatment of 2 with HBF₄ gave the BF₂-capped compound [Pd{(1)₂BF ₂}](μ-Cl)₂ (7). The solid-state structure of 7 containing a PdP₂O₂B metallacycle has been determined. Chloride abstraction of 7 with AgBF₄ in acetone/water afforded the aqua compound [Pd{(1)₂BF₂}(H₂O) ₂][BF₄] (8) that reacted with [NH₄] ₂[WS₄] to give [Pd{(1)₂BF₂} ₂]₂[μ-WS₄] (9). The average Pd-S and W-S distances in 9 are 2.385(3) and 2,189(3) Å, respectively. Treatment of [(η⁶-p-cymene)RuCl₂]₂ with 1H afforded the phosphinous acid adduct (η⁶-p-cymene)RuCl₂(1H) (10). Reduction of [Cp*RuCl₂]_x (Cp* = η⁵-C₅Me₅) with Zn followed by treatment with 1H resulted in the formation of the Zn(II) phosphinate complex [{Cp*Ru(η⁶-C₆H₅)} ^tBuPO₂}]₂(ZnCl₂)₂ (11) that contains a Zn₂O₄P₂ eight-membered ring.

Original language	English
Pages (from-to)	4921-4926
Number of pages	6
Journal	Inorganic Chemistry
Volume	43
Issue number	16
DOIs	https://doi.org/10.1021/ic049744u
Publication status	Published - 09 Aug 2004

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@article{44b08e8384dc4ce3916d0d7331c16e98,

title = "Chiral bisphosphinite metalloligands derived from a P-chiral secondary phosphine oxide",

abstract = "Interaction of PdCl2(MeCN)2 with 2 equiv of (S p)-tBuPhP(O)H (1H) followed by treatment with Et 3N gave [Pd-{(1)2H}]2(μ-Cl)2 (2). Reaction of 2 with Na[S2CNEt2] or K[N(PPh 2S)2] afforded Pd[(1)2H](S2CNEt 2) (3) or Pd[(1)2H)-[N(PPh2S)2] (4), respectively. Treatment of 3 with V(O)(acac)2 (acac = acetylacetonate) and CuSO4 in the presence of Et3N afforded bimetallic complexes V(O)[Pd(1)2(S2CNEt 2)]2 (5) or Cu[Pd(1)2(S2CNEt 2)]2 (6), respectively. X-ray crystallography established the Sp configuration for the phosphinous acid ligands in 3 and 6, indicating that 1H binds to Pd(II) with retention of configuration at phosphorus. The geometry around Cu in 6 is approximately square planar with the average Cu-O distance of 1.915(3) {\AA}. Treatment of 2 with HBF4 gave the BF2-capped compound [Pd{(1)2BF 2}](μ-Cl)2 (7). The solid-state structure of 7 containing a PdP2O2B metallacycle has been determined. Chloride abstraction of 7 with AgBF4 in acetone/water afforded the aqua compound [Pd{(1)2BF2}(H2O) 2][BF4] (8) that reacted with [NH4] 2[WS4] to give [Pd{(1)2BF2} 2]2[μ-WS4] (9). The average Pd-S and W-S distances in 9 are 2.385(3) and 2,189(3) {\AA}, respectively. Treatment of [(η6-p-cymene)RuCl2]2 with 1H afforded the phosphinous acid adduct (η6-p-cymene)RuCl2(1H) (10). Reduction of [Cp*RuCl2]x (Cp* = η5-C5Me5) with Zn followed by treatment with 1H resulted in the formation of the Zn(II) phosphinate complex [{Cp*Ru(η6-C6H5)} tBuPO2}]2(ZnCl2)2 (11) that contains a Zn2O4P2 eight-membered ring.",

author = "Chan, {Eddie Y.Y.} and Zhang, {Qian Feng} and Sau, {Yiu Keung} and Lo, {Samuel M.F.} and Sung, {Herman H.Y.} and Williams, {Ian D.} and Haynes, {Richard K.} and Leung, {Wa Hung}",

year = "2004",

month = aug,

day = "9",

doi = "10.1021/ic049744u",

language = "English",

volume = "43",

pages = "4921--4926",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "16",

}

TY - JOUR

T1 - Chiral bisphosphinite metalloligands derived from a P-chiral secondary phosphine oxide

AU - Chan, Eddie Y.Y.

AU - Zhang, Qian Feng

AU - Sau, Yiu Keung

AU - Lo, Samuel M.F.

AU - Sung, Herman H.Y.

AU - Williams, Ian D.

AU - Haynes, Richard K.

AU - Leung, Wa Hung

PY - 2004/8/9

Y1 - 2004/8/9

N2 - Interaction of PdCl2(MeCN)2 with 2 equiv of (S p)-tBuPhP(O)H (1H) followed by treatment with Et 3N gave [Pd-{(1)2H}]2(μ-Cl)2 (2). Reaction of 2 with Na[S2CNEt2] or K[N(PPh 2S)2] afforded Pd[(1)2H](S2CNEt 2) (3) or Pd[(1)2H)-[N(PPh2S)2] (4), respectively. Treatment of 3 with V(O)(acac)2 (acac = acetylacetonate) and CuSO4 in the presence of Et3N afforded bimetallic complexes V(O)[Pd(1)2(S2CNEt 2)]2 (5) or Cu[Pd(1)2(S2CNEt 2)]2 (6), respectively. X-ray crystallography established the Sp configuration for the phosphinous acid ligands in 3 and 6, indicating that 1H binds to Pd(II) with retention of configuration at phosphorus. The geometry around Cu in 6 is approximately square planar with the average Cu-O distance of 1.915(3) Å. Treatment of 2 with HBF4 gave the BF2-capped compound [Pd{(1)2BF 2}](μ-Cl)2 (7). The solid-state structure of 7 containing a PdP2O2B metallacycle has been determined. Chloride abstraction of 7 with AgBF4 in acetone/water afforded the aqua compound [Pd{(1)2BF2}(H2O) 2][BF4] (8) that reacted with [NH4] 2[WS4] to give [Pd{(1)2BF2} 2]2[μ-WS4] (9). The average Pd-S and W-S distances in 9 are 2.385(3) and 2,189(3) Å, respectively. Treatment of [(η6-p-cymene)RuCl2]2 with 1H afforded the phosphinous acid adduct (η6-p-cymene)RuCl2(1H) (10). Reduction of [Cp*RuCl2]x (Cp* = η5-C5Me5) with Zn followed by treatment with 1H resulted in the formation of the Zn(II) phosphinate complex [{Cp*Ru(η6-C6H5)} tBuPO2}]2(ZnCl2)2 (11) that contains a Zn2O4P2 eight-membered ring.

AB - Interaction of PdCl2(MeCN)2 with 2 equiv of (S p)-tBuPhP(O)H (1H) followed by treatment with Et 3N gave [Pd-{(1)2H}]2(μ-Cl)2 (2). Reaction of 2 with Na[S2CNEt2] or K[N(PPh 2S)2] afforded Pd[(1)2H](S2CNEt 2) (3) or Pd[(1)2H)-[N(PPh2S)2] (4), respectively. Treatment of 3 with V(O)(acac)2 (acac = acetylacetonate) and CuSO4 in the presence of Et3N afforded bimetallic complexes V(O)[Pd(1)2(S2CNEt 2)]2 (5) or Cu[Pd(1)2(S2CNEt 2)]2 (6), respectively. X-ray crystallography established the Sp configuration for the phosphinous acid ligands in 3 and 6, indicating that 1H binds to Pd(II) with retention of configuration at phosphorus. The geometry around Cu in 6 is approximately square planar with the average Cu-O distance of 1.915(3) Å. Treatment of 2 with HBF4 gave the BF2-capped compound [Pd{(1)2BF 2}](μ-Cl)2 (7). The solid-state structure of 7 containing a PdP2O2B metallacycle has been determined. Chloride abstraction of 7 with AgBF4 in acetone/water afforded the aqua compound [Pd{(1)2BF2}(H2O) 2][BF4] (8) that reacted with [NH4] 2[WS4] to give [Pd{(1)2BF2} 2]2[μ-WS4] (9). The average Pd-S and W-S distances in 9 are 2.385(3) and 2,189(3) Å, respectively. Treatment of [(η6-p-cymene)RuCl2]2 with 1H afforded the phosphinous acid adduct (η6-p-cymene)RuCl2(1H) (10). Reduction of [Cp*RuCl2]x (Cp* = η5-C5Me5) with Zn followed by treatment with 1H resulted in the formation of the Zn(II) phosphinate complex [{Cp*Ru(η6-C6H5)} tBuPO2}]2(ZnCl2)2 (11) that contains a Zn2O4P2 eight-membered ring.

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U2 - 10.1021/ic049744u

DO - 10.1021/ic049744u

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SN - 0020-1669

VL - 43

SP - 4921

EP - 4926

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 16

ER -

Chiral bisphosphinite metalloligands derived from a P-chiral secondary phosphine oxide

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