Synthesis, structure and bonding situation of [(dcpe)Pt(InCp*)2] and {((dcpe)Pt[GaC(SiMe3)3]2} - Two novel examples of platinum complexes of low valent group 13 metal species

Dana Weiß; Manuela Winter; Klaus Merz; Annegret Knüfer; Roland A. Fischer; Nikolaus Fröhlich; Gernot Frenking

doi:10.1016/S0277-5387(01)01027-0

Synthesis, structure and bonding situation of [(dcpe)Pt(InCp*)₂] and {((dcpe)Pt[GaC(SiMe₃)₃]₂} - Two novel examples of platinum complexes of low valent group 13 metal species

Dana Weiß, Manuela Winter, Klaus Merz, Annegret Knüfer, Roland A. Fischer, Nikolaus Fröhlich, Gernot Frenking

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

34 Scopus citations

Abstract

In analogy to the corresponding Cp*Al- and Cp*Ga-compounds two further bis(phosphine)platinum complexes [(dcpe)Pt(InCp*)₂] (1(In)) and {((dcpe)Pt[GaC(SiMe₃)₃]₂} (2(Ga)) containing monovalent Group 13 metal species as ligands are accessible by thermal activation of [(dcpe)Pt(H)(CH₂t-Bu)] (dcpe = bis(dicyclohexylphosphino)ethane) followed by the reaction with 2 equiv. of InCp* (Cp* = pentamethylcyclopentadienyl) or GaC(SiMe₃)₃. The crystal structure analysis reveals a distorted tetrahedral coordination of the platinum center for both compounds. The Pt-In distances in 1(In) amount to 2.569(1) and 2.556(1) Å. The Pt-Ga distances in 2(Ga) are exceptionally short and amount to 2.315(1) and 2.318(1) Å. Comparative theoretical investigations have been performed on this type of complexes and allow a deeper insight in the bonding situation. The NBO analysis reveals a significantly larger Pt → Ga π-back-donation for the model compound {(dhpe)Pt[GaC(SiH₃)₃]₂} (2M(Ga)) (0.44 e; dhpe = 1,2-diphosphinoethane) in comparison with the related model compound [(dhpe)Pt(GaCP)₂] (1M(Ga)) (0.29 e) bearing a strong π-donating organic ligand at the Ga center. A similar trend is observed for the Pt-Ga bond dissociation energies (D_e= 33.0 kcal mol^-1 for 2M(Ga), D_e = 18.3 kcal mol^-1 for 1M(Ga)). For the model compound [(dhpe)Pt(InCp)₂] (1M(In)) a value of D_e= 19.1 kcal mol^-1 has been calculated.

Original language	English
Pages (from-to)	535-542
Number of pages	8
Journal	Polyhedron
Volume	21
Issue number	5-6
DOIs	https://doi.org/10.1016/S0277-5387(01)01027-0
State	Published - 15 Mar 2002
Externally published	Yes

Keywords

Gallium
Heterobimetallic complexes
Indium
Platinum
Quantum chemical calculations
X-ray structure analysis

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10.1016/S0277-5387(01)01027-0

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@article{215eeb8e0ff64d71ae0aab3a1487ba8c,

title = "Synthesis, structure and bonding situation of [(dcpe)Pt(InCp*)2] and {((dcpe)Pt[GaC(SiMe3)3]2} - Two novel examples of platinum complexes of low valent group 13 metal species",

abstract = "In analogy to the corresponding Cp*Al- and Cp*Ga-compounds two further bis(phosphine)platinum complexes [(dcpe)Pt(InCp*)2] (1(In)) and {((dcpe)Pt[GaC(SiMe3)3]2} (2(Ga)) containing monovalent Group 13 metal species as ligands are accessible by thermal activation of [(dcpe)Pt(H)(CH2t-Bu)] (dcpe = bis(dicyclohexylphosphino)ethane) followed by the reaction with 2 equiv. of InCp* (Cp* = pentamethylcyclopentadienyl) or GaC(SiMe3)3. The crystal structure analysis reveals a distorted tetrahedral coordination of the platinum center for both compounds. The Pt-In distances in 1(In) amount to 2.569(1) and 2.556(1) {\AA}. The Pt-Ga distances in 2(Ga) are exceptionally short and amount to 2.315(1) and 2.318(1) {\AA}. Comparative theoretical investigations have been performed on this type of complexes and allow a deeper insight in the bonding situation. The NBO analysis reveals a significantly larger Pt → Ga π-back-donation for the model compound {(dhpe)Pt[GaC(SiH3)3]2} (2M(Ga)) (0.44 e; dhpe = 1,2-diphosphinoethane) in comparison with the related model compound [(dhpe)Pt(GaCP)2] (1M(Ga)) (0.29 e) bearing a strong π-donating organic ligand at the Ga center. A similar trend is observed for the Pt-Ga bond dissociation energies (De= 33.0 kcal mol-1 for 2M(Ga), De = 18.3 kcal mol-1 for 1M(Ga)). For the model compound [(dhpe)Pt(InCp)2] (1M(In)) a value of De= 19.1 kcal mol-1 has been calculated.",

keywords = "Gallium, Heterobimetallic complexes, Indium, Platinum, Quantum chemical calculations, X-ray structure analysis",

author = "Dana Wei{\ss} and Manuela Winter and Klaus Merz and Annegret Kn{\"u}fer and Fischer, {Roland A.} and Nikolaus Fr{\"o}hlich and Gernot Frenking",

note = "Funding Information: The support of this work by the Degussa AG and the W.C. Heraeus GmbH is gratefully acknowledged. We also thank the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie for financial support. ",

year = "2002",

month = mar,

day = "15",

doi = "10.1016/S0277-5387(01)01027-0",

language = "English",

volume = "21",

pages = "535--542",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier Ltd.",

number = "5-6",

}

TY - JOUR

T1 - Synthesis, structure and bonding situation of [(dcpe)Pt(InCp*)2] and {((dcpe)Pt[GaC(SiMe3)3]2} - Two novel examples of platinum complexes of low valent group 13 metal species

AU - Weiß, Dana

AU - Winter, Manuela

AU - Merz, Klaus

AU - Knüfer, Annegret

AU - Fischer, Roland A.

AU - Fröhlich, Nikolaus

AU - Frenking, Gernot

N1 - Funding Information: The support of this work by the Degussa AG and the W.C. Heraeus GmbH is gratefully acknowledged. We also thank the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie for financial support.

PY - 2002/3/15

Y1 - 2002/3/15

N2 - In analogy to the corresponding Cp*Al- and Cp*Ga-compounds two further bis(phosphine)platinum complexes [(dcpe)Pt(InCp*)2] (1(In)) and {((dcpe)Pt[GaC(SiMe3)3]2} (2(Ga)) containing monovalent Group 13 metal species as ligands are accessible by thermal activation of [(dcpe)Pt(H)(CH2t-Bu)] (dcpe = bis(dicyclohexylphosphino)ethane) followed by the reaction with 2 equiv. of InCp* (Cp* = pentamethylcyclopentadienyl) or GaC(SiMe3)3. The crystal structure analysis reveals a distorted tetrahedral coordination of the platinum center for both compounds. The Pt-In distances in 1(In) amount to 2.569(1) and 2.556(1) Å. The Pt-Ga distances in 2(Ga) are exceptionally short and amount to 2.315(1) and 2.318(1) Å. Comparative theoretical investigations have been performed on this type of complexes and allow a deeper insight in the bonding situation. The NBO analysis reveals a significantly larger Pt → Ga π-back-donation for the model compound {(dhpe)Pt[GaC(SiH3)3]2} (2M(Ga)) (0.44 e; dhpe = 1,2-diphosphinoethane) in comparison with the related model compound [(dhpe)Pt(GaCP)2] (1M(Ga)) (0.29 e) bearing a strong π-donating organic ligand at the Ga center. A similar trend is observed for the Pt-Ga bond dissociation energies (De= 33.0 kcal mol-1 for 2M(Ga), De = 18.3 kcal mol-1 for 1M(Ga)). For the model compound [(dhpe)Pt(InCp)2] (1M(In)) a value of De= 19.1 kcal mol-1 has been calculated.

AB - In analogy to the corresponding Cp*Al- and Cp*Ga-compounds two further bis(phosphine)platinum complexes [(dcpe)Pt(InCp*)2] (1(In)) and {((dcpe)Pt[GaC(SiMe3)3]2} (2(Ga)) containing monovalent Group 13 metal species as ligands are accessible by thermal activation of [(dcpe)Pt(H)(CH2t-Bu)] (dcpe = bis(dicyclohexylphosphino)ethane) followed by the reaction with 2 equiv. of InCp* (Cp* = pentamethylcyclopentadienyl) or GaC(SiMe3)3. The crystal structure analysis reveals a distorted tetrahedral coordination of the platinum center for both compounds. The Pt-In distances in 1(In) amount to 2.569(1) and 2.556(1) Å. The Pt-Ga distances in 2(Ga) are exceptionally short and amount to 2.315(1) and 2.318(1) Å. Comparative theoretical investigations have been performed on this type of complexes and allow a deeper insight in the bonding situation. The NBO analysis reveals a significantly larger Pt → Ga π-back-donation for the model compound {(dhpe)Pt[GaC(SiH3)3]2} (2M(Ga)) (0.44 e; dhpe = 1,2-diphosphinoethane) in comparison with the related model compound [(dhpe)Pt(GaCP)2] (1M(Ga)) (0.29 e) bearing a strong π-donating organic ligand at the Ga center. A similar trend is observed for the Pt-Ga bond dissociation energies (De= 33.0 kcal mol-1 for 2M(Ga), De = 18.3 kcal mol-1 for 1M(Ga)). For the model compound [(dhpe)Pt(InCp)2] (1M(In)) a value of De= 19.1 kcal mol-1 has been calculated.

KW - Gallium

KW - Heterobimetallic complexes

KW - Indium

KW - Platinum

KW - Quantum chemical calculations

KW - X-ray structure analysis

UR - http://www.scopus.com/inward/record.url?scp=0012352141&partnerID=8YFLogxK

U2 - 10.1016/S0277-5387(01)01027-0

DO - 10.1016/S0277-5387(01)01027-0

M3 - Article

AN - SCOPUS:0012352141

SN - 0277-5387

VL - 21

SP - 535

EP - 542

JO - Polyhedron

JF - Polyhedron

IS - 5-6

ER -

Synthesis, structure and bonding situation of [(dcpe)Pt(InCp*)₂] and {((dcpe)Pt[GaC(SiMe₃)₃]₂} - Two novel examples of platinum complexes of low valent group 13 metal species

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