Cationic binuclear trihydride complexes of platinum. A fluxional behavior for bridging and terminal hydrido ligands. Crystal and molecular structure of [Pt2H3{(t-Bu)2P(CH2)3P(t-Bu)2}2][B(C6H5)4]

T. H. Tulip, R. D. Wilson, James A. Ibers, T. Yamagata, T. Yoshida, Sei Otsuka

Research output: Contribution to journalArticle

69 Citations (Scopus)

Abstract

A series of complexes of bis(diphosphine)trihydridodiplatinum(II) cations have been prepared from the corresponding mononuclear cis-(diphosphine)dihydridoplatinum(II) or dimeric bis(diphosphine)diplatinum(0) compexes. These complexes are very stable. While their IR spectra are consistent with the presence of both terminal and bridging hydrido ligands, the NMR spectra are consistent with only one form of hydride coordination and show equivalence within the sets of H, P, and Pt atoms. These results suggest a rapid exchange of bridging and terminal hydrido ligands. The static molecular structure is proposed to involve one bridging and two terminal hydrido ligands. The complex [Pt2H3{(t-Bu)2P-(CH2)3P(t-Bu)2)2] [B(C6H5)4] crystallizes in space group C2h 5-P21/c with four formula units in a cell of dimensions a = 19.41 (1) Å, b = 18.03 (1) Å, c = 21.51 (1) Å, and β = 120.57 (3)°. The complex is sensitive to X radiation as evidenced by its progressive decomposition during data collection. Three data subsets on different crystals were acquired and merged to yield a total of 3468 unique reflections having Fo 2> 3σ(Fo 2). Least-squares refinement, including anisotropic thermal parameters for Pt and P atoms but isotropic parameters for the other nonhydrogen atoms, led to final conventional agreement indices (on F) of R = 0.081 and Rw= 0.101. The hydrido ligands were not located, but their positions are inferred from the coordination geometries of the Pt atoms. The Pt-Pt separation is 2.768 (2) Å and the dihedral angle between the two P-Pt-P coordination planes is 89°. The spectral and structural details, as well as those of the fluxional process, are discussed and related to those of similar mono-and binuclear platinum complexes.

Original languageEnglish (US)
Pages (from-to)2239-2250
Number of pages12
JournalInorganic chemistry
Volume18
Issue number8
DOIs
StatePublished - Feb 1 1979

Fingerprint

Platinum
Molecular structure
platinum
molecular structure
Crystal structure
Ligands
Atoms
ligands
crystal structure
atoms
Dihedral angle
Hydrides
set theory
hydrides
equivalence
dihedral angle
Cations
Ion exchange
Nuclear magnetic resonance
Decomposition

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

@article{d75344fa89fb4ee2a3ac5a531a85d7c4,
title = "Cationic binuclear trihydride complexes of platinum. A fluxional behavior for bridging and terminal hydrido ligands. Crystal and molecular structure of [Pt2H3{(t-Bu)2P(CH2)3P(t-Bu)2}2][B(C6H5)4]",
abstract = "A series of complexes of bis(diphosphine)trihydridodiplatinum(II) cations have been prepared from the corresponding mononuclear cis-(diphosphine)dihydridoplatinum(II) or dimeric bis(diphosphine)diplatinum(0) compexes. These complexes are very stable. While their IR spectra are consistent with the presence of both terminal and bridging hydrido ligands, the NMR spectra are consistent with only one form of hydride coordination and show equivalence within the sets of H, P, and Pt atoms. These results suggest a rapid exchange of bridging and terminal hydrido ligands. The static molecular structure is proposed to involve one bridging and two terminal hydrido ligands. The complex [Pt2H3{(t-Bu)2P-(CH2)3P(t-Bu)2)2] [B(C6H5)4] crystallizes in space group C2h 5-P21/c with four formula units in a cell of dimensions a = 19.41 (1) {\AA}, b = 18.03 (1) {\AA}, c = 21.51 (1) {\AA}, and β = 120.57 (3)°. The complex is sensitive to X radiation as evidenced by its progressive decomposition during data collection. Three data subsets on different crystals were acquired and merged to yield a total of 3468 unique reflections having Fo 2> 3σ(Fo 2). Least-squares refinement, including anisotropic thermal parameters for Pt and P atoms but isotropic parameters for the other nonhydrogen atoms, led to final conventional agreement indices (on F) of R = 0.081 and Rw= 0.101. The hydrido ligands were not located, but their positions are inferred from the coordination geometries of the Pt atoms. The Pt-Pt separation is 2.768 (2) {\AA} and the dihedral angle between the two P-Pt-P coordination planes is 89°. The spectral and structural details, as well as those of the fluxional process, are discussed and related to those of similar mono-and binuclear platinum complexes.",
author = "Tulip, {T. H.} and Wilson, {R. D.} and Ibers, {James A.} and T. Yamagata and T. Yoshida and Sei Otsuka",
year = "1979",
month = "2",
day = "1",
doi = "10.1021/ic50198a039",
language = "English (US)",
volume = "18",
pages = "2239--2250",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "8",

}

TY - JOUR

T1 - Cationic binuclear trihydride complexes of platinum. A fluxional behavior for bridging and terminal hydrido ligands. Crystal and molecular structure of [Pt2H3{(t-Bu)2P(CH2)3P(t-Bu)2}2][B(C6H5)4]

AU - Tulip, T. H.

AU - Wilson, R. D.

AU - Ibers, James A.

AU - Yamagata, T.

AU - Yoshida, T.

AU - Otsuka, Sei

PY - 1979/2/1

Y1 - 1979/2/1

N2 - A series of complexes of bis(diphosphine)trihydridodiplatinum(II) cations have been prepared from the corresponding mononuclear cis-(diphosphine)dihydridoplatinum(II) or dimeric bis(diphosphine)diplatinum(0) compexes. These complexes are very stable. While their IR spectra are consistent with the presence of both terminal and bridging hydrido ligands, the NMR spectra are consistent with only one form of hydride coordination and show equivalence within the sets of H, P, and Pt atoms. These results suggest a rapid exchange of bridging and terminal hydrido ligands. The static molecular structure is proposed to involve one bridging and two terminal hydrido ligands. The complex [Pt2H3{(t-Bu)2P-(CH2)3P(t-Bu)2)2] [B(C6H5)4] crystallizes in space group C2h 5-P21/c with four formula units in a cell of dimensions a = 19.41 (1) Å, b = 18.03 (1) Å, c = 21.51 (1) Å, and β = 120.57 (3)°. The complex is sensitive to X radiation as evidenced by its progressive decomposition during data collection. Three data subsets on different crystals were acquired and merged to yield a total of 3468 unique reflections having Fo 2> 3σ(Fo 2). Least-squares refinement, including anisotropic thermal parameters for Pt and P atoms but isotropic parameters for the other nonhydrogen atoms, led to final conventional agreement indices (on F) of R = 0.081 and Rw= 0.101. The hydrido ligands were not located, but their positions are inferred from the coordination geometries of the Pt atoms. The Pt-Pt separation is 2.768 (2) Å and the dihedral angle between the two P-Pt-P coordination planes is 89°. The spectral and structural details, as well as those of the fluxional process, are discussed and related to those of similar mono-and binuclear platinum complexes.

AB - A series of complexes of bis(diphosphine)trihydridodiplatinum(II) cations have been prepared from the corresponding mononuclear cis-(diphosphine)dihydridoplatinum(II) or dimeric bis(diphosphine)diplatinum(0) compexes. These complexes are very stable. While their IR spectra are consistent with the presence of both terminal and bridging hydrido ligands, the NMR spectra are consistent with only one form of hydride coordination and show equivalence within the sets of H, P, and Pt atoms. These results suggest a rapid exchange of bridging and terminal hydrido ligands. The static molecular structure is proposed to involve one bridging and two terminal hydrido ligands. The complex [Pt2H3{(t-Bu)2P-(CH2)3P(t-Bu)2)2] [B(C6H5)4] crystallizes in space group C2h 5-P21/c with four formula units in a cell of dimensions a = 19.41 (1) Å, b = 18.03 (1) Å, c = 21.51 (1) Å, and β = 120.57 (3)°. The complex is sensitive to X radiation as evidenced by its progressive decomposition during data collection. Three data subsets on different crystals were acquired and merged to yield a total of 3468 unique reflections having Fo 2> 3σ(Fo 2). Least-squares refinement, including anisotropic thermal parameters for Pt and P atoms but isotropic parameters for the other nonhydrogen atoms, led to final conventional agreement indices (on F) of R = 0.081 and Rw= 0.101. The hydrido ligands were not located, but their positions are inferred from the coordination geometries of the Pt atoms. The Pt-Pt separation is 2.768 (2) Å and the dihedral angle between the two P-Pt-P coordination planes is 89°. The spectral and structural details, as well as those of the fluxional process, are discussed and related to those of similar mono-and binuclear platinum complexes.

UR - http://www.scopus.com/inward/record.url?scp=33845560372&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33845560372&partnerID=8YFLogxK

U2 - 10.1021/ic50198a039

DO - 10.1021/ic50198a039

M3 - Article

VL - 18

SP - 2239

EP - 2250

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 8

ER -