Formation of a Chelating σ-Ally I by the Intramolecular Activation of a Cyclopropylphosphine. Synthesis and Crystal Structure of [PdCI(P(t-Bu)2CH=C(CH3)CH2)]2

Wiley J. Youngs; James Mahood; Barbara L. Simms; Paul N. Swepston; James A Ibers; Shang Maoyu; Huang Jinling; Lu Jiaxi

doi:10.1021/om50001a026

Formation of a Chelating σ-Ally I by the Intramolecular Activation of a Cyclopropylphosphine. Synthesis and Crystal Structure of [PdCI(P(t-Bu)₂CH=C(CH₃)CH₂)]₂

Wiley J. Youngs, James Mahood, Barbara L. Simms, Paul N. Swepston, James A Ibers^*, Shang Maoyu, Huang Jinling, Lu Jiaxi

^*Corresponding author for this work

Chemistry

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Abstract

The cyclopropyl-containing phosphine di-tert-butyl(cyclopropylmethyl)phosphine, P(t-Bu₂CH₂- CHCH₂CH₂, reacts with PdCl₂ to afford trans-PdCl₂(P(t-Bu)₂CH₂CHCH₂CH₂)₂. When this complex is refluxed in MeOCH₂CH₂OH or glacial acetic acid, a cyclometalated dimer, [PdCl(P(t-Bu)₂CH=C- (CH₃)CH₂)]₂, is formed, as deduced from spectroscopic and X-ray analysis. This complex crystallizes in the monoclinic space group C₂h₅P2₁/n (a = 7.957 (4) Å, b = 15.780 (2) Å,_c = 12.169 (1) Å, and β = 99.11 (2)) with two molecules per unit cell (imposed crystallographic symmetry, 1). The final agreement indices for 2493 reflections having F₀ ² > 3σ(F₀ ²) are R(F) = 0.031 and R_w(F) = 0.041 (136 variables). The five-atom chelate ring PdP°C=C°C is planar to within 0.011 (4) Å with a bond length pattern of PdP = 2.218 (1) Å, P°C = 1.781 (4) Å, C=C = 1.328 (5) Å, C°C = 1.493 (5) Å, and CPd = 2.016 (3) Å. The Pd-Cl distance trans to the P atom is 2.416 (1) Å and that trans to the C atom is 2.457 (1) Å. In the formation of the complex the chelating σ-allyl group probably results from C-C bond activation of the cyclopropyl group.

Original language	English (US)
Pages (from-to)	917-921
Number of pages	5
Journal	Organometallics
Volume	2
Issue number	7
DOIs	https://doi.org/10.1021/om50001a026
State	Published - Jan 1 1983

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Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{d32fc72436c24969a1d26e97e40d7b78,

title = "Formation of a Chelating σ-Ally I by the Intramolecular Activation of a Cyclopropylphosphine. Synthesis and Crystal Structure of [PdCI(P(t-Bu)2CH=C(CH3)CH2)]2 ",

abstract = "The cyclopropyl-containing phosphine di-tert-butyl(cyclopropylmethyl)phosphine, P(t-Bu2CH2- CHCH2CH2, reacts with PdCl2 to afford trans-PdCl2(P(t-Bu)2CH2CHCH2CH2)2. When this complex is refluxed in MeOCH2CH2OH or glacial acetic acid, a cyclometalated dimer, [PdCl(P(t-Bu)2CH=C- (CH3)CH2)]2, is formed, as deduced from spectroscopic and X-ray analysis. This complex crystallizes in the monoclinic space group C2h5P21/n (a = 7.957 (4) {\AA}, b = 15.780 (2) {\AA},_c = 12.169 (1) {\AA}, and β = 99.11 (2)) with two molecules per unit cell (imposed crystallographic symmetry, 1). The final agreement indices for 2493 reflections having F0 2 > 3σ(F0 2) are R(F) = 0.031 and Rw(F) = 0.041 (136 variables). The five-atom chelate ring PdP°C=C°C is planar to within 0.011 (4) {\AA} with a bond length pattern of PdP = 2.218 (1) {\AA}, P°C = 1.781 (4) {\AA}, C=C = 1.328 (5) {\AA}, C°C = 1.493 (5) {\AA}, and CPd = 2.016 (3) {\AA}. The Pd-Cl distance trans to the P atom is 2.416 (1) {\AA} and that trans to the C atom is 2.457 (1) {\AA}. In the formation of the complex the chelating σ-allyl group probably results from C-C bond activation of the cyclopropyl group.",

author = "Youngs, {Wiley J.} and James Mahood and Simms, {Barbara L.} and Swepston, {Paul N.} and Ibers, {James A} and Shang Maoyu and Huang Jinling and Lu Jiaxi",

year = "1983",

month = jan,

day = "1",

doi = "10.1021/om50001a026",

language = "English (US)",

volume = "2",

pages = "917--921",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "7",

}

TY - JOUR

T1 - Formation of a Chelating σ-Ally I by the Intramolecular Activation of a Cyclopropylphosphine. Synthesis and Crystal Structure of [PdCI(P(t-Bu)2CH=C(CH3)CH2)]2

AU - Youngs, Wiley J.

AU - Mahood, James

AU - Simms, Barbara L.

AU - Swepston, Paul N.

AU - Ibers, James A

AU - Maoyu, Shang

AU - Jinling, Huang

AU - Jiaxi, Lu

PY - 1983/1/1

Y1 - 1983/1/1

N2 - The cyclopropyl-containing phosphine di-tert-butyl(cyclopropylmethyl)phosphine, P(t-Bu2CH2- CHCH2CH2, reacts with PdCl2 to afford trans-PdCl2(P(t-Bu)2CH2CHCH2CH2)2. When this complex is refluxed in MeOCH2CH2OH or glacial acetic acid, a cyclometalated dimer, [PdCl(P(t-Bu)2CH=C- (CH3)CH2)]2, is formed, as deduced from spectroscopic and X-ray analysis. This complex crystallizes in the monoclinic space group C2h5P21/n (a = 7.957 (4) Å, b = 15.780 (2) Å,_c = 12.169 (1) Å, and β = 99.11 (2)) with two molecules per unit cell (imposed crystallographic symmetry, 1). The final agreement indices for 2493 reflections having F0 2 > 3σ(F0 2) are R(F) = 0.031 and Rw(F) = 0.041 (136 variables). The five-atom chelate ring PdP°C=C°C is planar to within 0.011 (4) Å with a bond length pattern of PdP = 2.218 (1) Å, P°C = 1.781 (4) Å, C=C = 1.328 (5) Å, C°C = 1.493 (5) Å, and CPd = 2.016 (3) Å. The Pd-Cl distance trans to the P atom is 2.416 (1) Å and that trans to the C atom is 2.457 (1) Å. In the formation of the complex the chelating σ-allyl group probably results from C-C bond activation of the cyclopropyl group.

AB - The cyclopropyl-containing phosphine di-tert-butyl(cyclopropylmethyl)phosphine, P(t-Bu2CH2- CHCH2CH2, reacts with PdCl2 to afford trans-PdCl2(P(t-Bu)2CH2CHCH2CH2)2. When this complex is refluxed in MeOCH2CH2OH or glacial acetic acid, a cyclometalated dimer, [PdCl(P(t-Bu)2CH=C- (CH3)CH2)]2, is formed, as deduced from spectroscopic and X-ray analysis. This complex crystallizes in the monoclinic space group C2h5P21/n (a = 7.957 (4) Å, b = 15.780 (2) Å,_c = 12.169 (1) Å, and β = 99.11 (2)) with two molecules per unit cell (imposed crystallographic symmetry, 1). The final agreement indices for 2493 reflections having F0 2 > 3σ(F0 2) are R(F) = 0.031 and Rw(F) = 0.041 (136 variables). The five-atom chelate ring PdP°C=C°C is planar to within 0.011 (4) Å with a bond length pattern of PdP = 2.218 (1) Å, P°C = 1.781 (4) Å, C=C = 1.328 (5) Å, C°C = 1.493 (5) Å, and CPd = 2.016 (3) Å. The Pd-Cl distance trans to the P atom is 2.416 (1) Å and that trans to the C atom is 2.457 (1) Å. In the formation of the complex the chelating σ-allyl group probably results from C-C bond activation of the cyclopropyl group.

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U2 - 10.1021/om50001a026

DO - 10.1021/om50001a026

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SN - 0276-7333

VL - 2

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JO - Organometallics

JF - Organometallics

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ER -

Formation of a Chelating σ-Ally I by the Intramolecular Activation of a Cyclopropylphosphine. Synthesis and Crystal Structure of [PdCI(P(t-Bu)₂CH=C(CH₃)CH₂)]₂

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