Synthesis and Reactivity of sigma-alkynyl/P-Bonded(phosphinoalkyne) platinum complexes towards cis-[M(C6F5)2(thf)2] (M = Pt, Pd)

The reactivity of cis-bis(alkynyl)bis((diphenylphosphino)alkyne)platinum(II) complexes cis-[Pt(C≡CR)2L2] (R = Ph, But; L = PPh2C≡CPh (L1), PPh2C≡CBut (L2); 1-4), formed by displacement of the COD ligand from [Pt(C≡CR)2(COD)], toward cis-[M(C6F5)2(thf)2] (M = Pt, Pd, thf = tetrahydrofuran; in both a...

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Autores: Ara, I. [0000-0002-5881-9698], Falvello, L.R. [0000-0002-0444-996X], Fernández, S., Forniés, J., Lalinde, E. [0000-0001-7402-1742], Martín, A., Moreno, M.T. [0000-0002-7744-9805]
Formato: artículo
Estado:Versión publicada
Fecha de publicación:1997
País:España
Recursos:Universidad de La Rioja (UR)
Repositorio:RIUR. Repositorio Institucional de la Universidad de La Rioja
OAI Identifier:oai:portal.dialnet.es:doc/5bbc691fb750603269e81597
Acesso em linha:https://investigacion.unirioja.es/documentos/5bbc691fb750603269e81597
Access Level:acceso abierto
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network_acronym_str ES
network_name_str España
repository_id_str
spelling Synthesis and Reactivity of sigma-alkynyl/P-Bonded(phosphinoalkyne) platinum complexes towards cis-[M(C6F5)2(thf)2] (M = Pt, Pd)Ara, I. [0000-0002-5881-9698]Falvello, L.R. [0000-0002-0444-996X]Fernández, S.Forniés, J.Lalinde, E. [0000-0001-7402-1742]Martín, A.Moreno, M.T. [0000-0002-7744-9805]The reactivity of cis-bis(alkynyl)bis((diphenylphosphino)alkyne)platinum(II) complexes cis-[Pt(C≡CR)2L2] (R = Ph, But; L = PPh2C≡CPh (L1), PPh2C≡CBut (L2); 1-4), formed by displacement of the COD ligand from [Pt(C≡CR)2(COD)], toward cis-[M(C6F5)2(thf)2] (M = Pt, Pd, thf = tetrahydrofuran; in both a 1:1 and 1:2 molar ratio) has been investigated. Treatment of 1-4 with 1 equiv of cis-[M(C6F5)2(thf)2] affords dinuclear derivatives [{L2Pt-(μ-η1:η2-C≡CR) 2}M(C6F5)2] (5-12) with exclusive formation of doubly alkynyl-bridged systems. The molecular structure of [{(ButC≡CPh2P)2Pt(μ-η 1:η2-C≡CPh)2}Pd(C6F 5)2], 10, is presented. In contrast, it was found that the course of the reactions with 2 equiv of cis-[M(C6F5)2(thf)2] strongly depend on the alkynyl substituents and metal centers. Thus, treatment of tert-butylalkynyl derivatives cis-[Pt(C≡CBut)2L2] (2, 4) with 2 equiv of cis-[M(C6F5)2(thf)2] (M = Pt, Pd) only gives the expected trinuclear complexes 15A and 18A, in the case of the reactions with cis-[Pt(C6F5)2(thf)2]. The molecular structure of the complex [{Pt(μ-κ(P):η2-PPh2C≡CPh) 2(μ-η1:η2-C≡CBu t)2}{Pt(C6F5)2} 2], 15A, reveals that both the complexed cis-Pt(C6F5)2 moieties are symmetrically linked to the precursor "cis-[Pt(C≡CBut)2-(PPh 2C≡CPh)2]", with the platinum atoms connected by two unusual mixed alkynyl/ phosphinoalkyne bridging systems. On the other hand, similar reactions of phenylethynyl derivatives (1, 3) with 2 equiv of cis-[Pd(C6F5)2(thf)2] and 3 (L = PPh2C≡CBut) with cis-[Pt-(C6F5)2(thf)2] lead, instead, to the unexpected trinuclear PtPd2 (14B, 17B) and Pt3 (16B) derivatives which display terminal phosphinoalkyne ligands and, hence, contain the alkynyl groups acting as μ3-η2 (σ-Pt edge Pd or Pt) bridging ligands. However, a mixture of both types of isomers 13A and 13B (50:32) is observed in the reaction system cis-[Pt(C≡CPh)2-(PPh2C≡CPh)2] (1)/cis-[Pt(C6F5)2(thf)2]. The following order of bonding capability is deduced from this study: alkynyl > P-bonded phosphinoalkyne and XC≡CPh fragments > XC≡CBut (X = Pt, P).1997info:eu-repo/semantics/articleSubtype: Articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttps://investigacion.unirioja.es/documentos/5bbc691fb750603269e81597reponame:RIUR. Repositorio Institucional de la Universidad de La Riojainstname:Universidad de La Rioja (UR)Inglésinfo:eu-repo/semantics/altIdentifier/doi/10.1021/OM970663Yinfo:eu-repo/semantics/altIdentifier/wos/WOS:000071423300051info:eu-repo/semantics/altIdentifier/pissn/0276-7333Synthesis and Reactivity of sigma-alkynyl/P-Bonded(phosphinoalkyne) platinum complexes towards cis-[M(C6F5)2(thf)2] (M = Pt, Pd), 1997, vol. 16, núm. 26, pág. 5923-5937info:eu-repo/semantics/openAccessoai:portal.dialnet.es:doc/5bbc691fb750603269e815972026-06-14T12:47:17Z
dc.title.none.fl_str_mv Synthesis and Reactivity of sigma-alkynyl/P-Bonded(phosphinoalkyne) platinum complexes towards cis-[M(C6F5)2(thf)2] (M = Pt, Pd)
title Synthesis and Reactivity of sigma-alkynyl/P-Bonded(phosphinoalkyne) platinum complexes towards cis-[M(C6F5)2(thf)2] (M = Pt, Pd)
spellingShingle Synthesis and Reactivity of sigma-alkynyl/P-Bonded(phosphinoalkyne) platinum complexes towards cis-[M(C6F5)2(thf)2] (M = Pt, Pd)
Ara, I. [0000-0002-5881-9698]
title_short Synthesis and Reactivity of sigma-alkynyl/P-Bonded(phosphinoalkyne) platinum complexes towards cis-[M(C6F5)2(thf)2] (M = Pt, Pd)
title_full Synthesis and Reactivity of sigma-alkynyl/P-Bonded(phosphinoalkyne) platinum complexes towards cis-[M(C6F5)2(thf)2] (M = Pt, Pd)
title_fullStr Synthesis and Reactivity of sigma-alkynyl/P-Bonded(phosphinoalkyne) platinum complexes towards cis-[M(C6F5)2(thf)2] (M = Pt, Pd)
title_full_unstemmed Synthesis and Reactivity of sigma-alkynyl/P-Bonded(phosphinoalkyne) platinum complexes towards cis-[M(C6F5)2(thf)2] (M = Pt, Pd)
title_sort Synthesis and Reactivity of sigma-alkynyl/P-Bonded(phosphinoalkyne) platinum complexes towards cis-[M(C6F5)2(thf)2] (M = Pt, Pd)
dc.creator.none.fl_str_mv Ara, I. [0000-0002-5881-9698]
Falvello, L.R. [0000-0002-0444-996X]
Fernández, S.
Forniés, J.
Lalinde, E. [0000-0001-7402-1742]
Martín, A.
Moreno, M.T. [0000-0002-7744-9805]
author Ara, I. [0000-0002-5881-9698]
author_facet Ara, I. [0000-0002-5881-9698]
Falvello, L.R. [0000-0002-0444-996X]
Fernández, S.
Forniés, J.
Lalinde, E. [0000-0001-7402-1742]
Martín, A.
Moreno, M.T. [0000-0002-7744-9805]
author_role author
author2 Falvello, L.R. [0000-0002-0444-996X]
Fernández, S.
Forniés, J.
Lalinde, E. [0000-0001-7402-1742]
Martín, A.
Moreno, M.T. [0000-0002-7744-9805]
author2_role author
author
author
author
author
author
description The reactivity of cis-bis(alkynyl)bis((diphenylphosphino)alkyne)platinum(II) complexes cis-[Pt(C≡CR)2L2] (R = Ph, But; L = PPh2C≡CPh (L1), PPh2C≡CBut (L2); 1-4), formed by displacement of the COD ligand from [Pt(C≡CR)2(COD)], toward cis-[M(C6F5)2(thf)2] (M = Pt, Pd, thf = tetrahydrofuran; in both a 1:1 and 1:2 molar ratio) has been investigated. Treatment of 1-4 with 1 equiv of cis-[M(C6F5)2(thf)2] affords dinuclear derivatives [{L2Pt-(μ-η1:η2-C≡CR) 2}M(C6F5)2] (5-12) with exclusive formation of doubly alkynyl-bridged systems. The molecular structure of [{(ButC≡CPh2P)2Pt(μ-η 1:η2-C≡CPh)2}Pd(C6F 5)2], 10, is presented. In contrast, it was found that the course of the reactions with 2 equiv of cis-[M(C6F5)2(thf)2] strongly depend on the alkynyl substituents and metal centers. Thus, treatment of tert-butylalkynyl derivatives cis-[Pt(C≡CBut)2L2] (2, 4) with 2 equiv of cis-[M(C6F5)2(thf)2] (M = Pt, Pd) only gives the expected trinuclear complexes 15A and 18A, in the case of the reactions with cis-[Pt(C6F5)2(thf)2]. The molecular structure of the complex [{Pt(μ-κ(P):η2-PPh2C≡CPh) 2(μ-η1:η2-C≡CBu t)2}{Pt(C6F5)2} 2], 15A, reveals that both the complexed cis-Pt(C6F5)2 moieties are symmetrically linked to the precursor "cis-[Pt(C≡CBut)2-(PPh 2C≡CPh)2]", with the platinum atoms connected by two unusual mixed alkynyl/ phosphinoalkyne bridging systems. On the other hand, similar reactions of phenylethynyl derivatives (1, 3) with 2 equiv of cis-[Pd(C6F5)2(thf)2] and 3 (L = PPh2C≡CBut) with cis-[Pt-(C6F5)2(thf)2] lead, instead, to the unexpected trinuclear PtPd2 (14B, 17B) and Pt3 (16B) derivatives which display terminal phosphinoalkyne ligands and, hence, contain the alkynyl groups acting as μ3-η2 (σ-Pt edge Pd or Pt) bridging ligands. However, a mixture of both types of isomers 13A and 13B (50:32) is observed in the reaction system cis-[Pt(C≡CPh)2-(PPh2C≡CPh)2] (1)/cis-[Pt(C6F5)2(thf)2]. The following order of bonding capability is deduced from this study: alkynyl > P-bonded phosphinoalkyne and XC≡CPh fragments > XC≡CBut (X = Pt, P).
publishDate 1997
dc.date.none.fl_str_mv 1997
dc.type.none.fl_str_mv info:eu-repo/semantics/article
Subtype: Article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv https://investigacion.unirioja.es/documentos/5bbc691fb750603269e81597
url https://investigacion.unirioja.es/documentos/5bbc691fb750603269e81597
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/OM970663Y
info:eu-repo/semantics/altIdentifier/wos/WOS:000071423300051
info:eu-repo/semantics/altIdentifier/pissn/0276-7333
Synthesis and Reactivity of sigma-alkynyl/P-Bonded(phosphinoalkyne) platinum complexes towards cis-[M(C6F5)2(thf)2] (M = Pt, Pd), 1997, vol. 16, núm. 26, pág. 5923-5937
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
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instname:Universidad de La Rioja (UR)
instname_str Universidad de La Rioja (UR)
reponame_str RIUR. Repositorio Institucional de la Universidad de La Rioja
collection RIUR. Repositorio Institucional de la Universidad de La Rioja
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