Roof-shaped halide-bridged bimetallic complexes via ring expansion reaction

Clarite Azerraf; Shmuel Cohen; Dmitri Gelman

doi:10.1021/ic060700q

Roof-shaped halide-bridged bimetallic complexes via ring expansion reaction

Clarite Azerraf, Shmuel Cohen, Dmitri Gelman^*

^*Corresponding author for this work

Institute of Chemistry

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

37 Scopus citations

Abstract

Binucleating behavior of rigid triptycene-based ligands has been studied. It has been demonstrated that trans-spanned transition-metal mononuclear complexes bearing 1,8-bis(diisopropylphosphino)triptycene (L1) and 1-diisopropylphosphino-8-diphenylphosphinotriptycene (L2) react with an appropriate transition-metal precursor via a ring-expansion pathway to form unusual bimetallic quasi-closed structures. New palladium and rhodium complexes featuring strongly bent (ca. 115°) M₂(μ-Cl₂) cores with very closely spanned metal centers (less than 3 Å) have been prepared using the described ring-expansion reaction and have been fully characterized. Despite a constrained arrangement of the binuclear system, halogen bridges in all new compounds were stable in both the solid state and solution showing no tendency for dissociation even in the presence of added Lewis bases. Spontaneous resolution of the dissymmetric Pd₂(μ-Cl)₂Cl ₂(1-diisopropylphosphino-8-diphenylphosphinotriptycene) (2) into enantiopure antipodes is discussed as well.

Original language	English
Pages (from-to)	7010-7017
Number of pages	8
Journal	Inorganic Chemistry
Volume	45
Issue number	17
DOIs	https://doi.org/10.1021/ic060700q
State	Published - 21 Aug 2006

Access to Document

10.1021/ic060700q

Cite this

@article{8b02cce1334c4f0aac9a2d4f40d1e7cc,

title = "Roof-shaped halide-bridged bimetallic complexes via ring expansion reaction",

abstract = "Binucleating behavior of rigid triptycene-based ligands has been studied. It has been demonstrated that trans-spanned transition-metal mononuclear complexes bearing 1,8-bis(diisopropylphosphino)triptycene (L1) and 1-diisopropylphosphino-8-diphenylphosphinotriptycene (L2) react with an appropriate transition-metal precursor via a ring-expansion pathway to form unusual bimetallic quasi-closed structures. New palladium and rhodium complexes featuring strongly bent (ca. 115°) M2(μ-Cl2) cores with very closely spanned metal centers (less than 3 {\AA}) have been prepared using the described ring-expansion reaction and have been fully characterized. Despite a constrained arrangement of the binuclear system, halogen bridges in all new compounds were stable in both the solid state and solution showing no tendency for dissociation even in the presence of added Lewis bases. Spontaneous resolution of the dissymmetric Pd2(μ-Cl)2Cl 2(1-diisopropylphosphino-8-diphenylphosphinotriptycene) (2) into enantiopure antipodes is discussed as well.",

author = "Clarite Azerraf and Shmuel Cohen and Dmitri Gelman",

year = "2006",

month = aug,

day = "21",

doi = "10.1021/ic060700q",

language = "אנגלית",

volume = "45",

pages = "7010--7017",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "17",

}

TY - JOUR

T1 - Roof-shaped halide-bridged bimetallic complexes via ring expansion reaction

AU - Azerraf, Clarite

AU - Cohen, Shmuel

AU - Gelman, Dmitri

PY - 2006/8/21

Y1 - 2006/8/21

N2 - Binucleating behavior of rigid triptycene-based ligands has been studied. It has been demonstrated that trans-spanned transition-metal mononuclear complexes bearing 1,8-bis(diisopropylphosphino)triptycene (L1) and 1-diisopropylphosphino-8-diphenylphosphinotriptycene (L2) react with an appropriate transition-metal precursor via a ring-expansion pathway to form unusual bimetallic quasi-closed structures. New palladium and rhodium complexes featuring strongly bent (ca. 115°) M2(μ-Cl2) cores with very closely spanned metal centers (less than 3 Å) have been prepared using the described ring-expansion reaction and have been fully characterized. Despite a constrained arrangement of the binuclear system, halogen bridges in all new compounds were stable in both the solid state and solution showing no tendency for dissociation even in the presence of added Lewis bases. Spontaneous resolution of the dissymmetric Pd2(μ-Cl)2Cl 2(1-diisopropylphosphino-8-diphenylphosphinotriptycene) (2) into enantiopure antipodes is discussed as well.

AB - Binucleating behavior of rigid triptycene-based ligands has been studied. It has been demonstrated that trans-spanned transition-metal mononuclear complexes bearing 1,8-bis(diisopropylphosphino)triptycene (L1) and 1-diisopropylphosphino-8-diphenylphosphinotriptycene (L2) react with an appropriate transition-metal precursor via a ring-expansion pathway to form unusual bimetallic quasi-closed structures. New palladium and rhodium complexes featuring strongly bent (ca. 115°) M2(μ-Cl2) cores with very closely spanned metal centers (less than 3 Å) have been prepared using the described ring-expansion reaction and have been fully characterized. Despite a constrained arrangement of the binuclear system, halogen bridges in all new compounds were stable in both the solid state and solution showing no tendency for dissociation even in the presence of added Lewis bases. Spontaneous resolution of the dissymmetric Pd2(μ-Cl)2Cl 2(1-diisopropylphosphino-8-diphenylphosphinotriptycene) (2) into enantiopure antipodes is discussed as well.

UR - http://www.scopus.com/inward/record.url?scp=33748589203&partnerID=8YFLogxK

U2 - 10.1021/ic060700q

DO - 10.1021/ic060700q

M3 - ???researchoutput.researchoutputtypes.contributiontojournal.article???

C2 - 16903761

AN - SCOPUS:33748589203

SN - 0020-1669

VL - 45

SP - 7010

EP - 7017

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 17

ER -

Roof-shaped halide-bridged bimetallic complexes via ring expansion reaction

Abstract

Access to Document

Other files and links

Fingerprint

Cite this