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

Clarite Azerraf, Shmuel Cohen, Dmitri Gelman*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

37 Scopus citations


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 languageAmerican English
Pages (from-to)7010-7017
Number of pages8
JournalInorganic Chemistry
Issue number17
StatePublished - 21 Aug 2006


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