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Heterobimetallic [3]trochrocenophanes with PdCl2andPtCl2bridges were prepared in reasonable yields. The PdCl2species possess, like their Pt analogues, poor solubilitybut can be made more soluble by ligand substitution. By reaction ofPd-bridged [3]trochrocenophanes with MeLi, both Cl atoms can be substitutedby a Me group. Likewise, reaction of Pt-bridged complexes with LiCCPhleads to the expected disubstituted compound. Herein we present thesynthesis of MCl2- and MR2-bridged (M = Pd,Pt; R = Me, CCPh) [3]trochrocenophanes, as well as some solid-statestructures of these [3]trochrocenophanes. [ABSTRACT FROM AUTHOR]

A reactivity study on a series of platinum boryl complexeswasperformed. The first stable base adducts of cationic haloboryl complexesof the form trans-[Pt{B(Br)(NMe2)}(NCMe)(PCy3)2]쇪 isolated and fully characterized.The dianion [B12Cl12]2–wasintroduced as a weakly coordinating anion to complex chemistry forminga A2X salt. Through the reaction of trans-[Pt{B(Br)(tBu)}Br(PCy3)2]with BBr2tBu, the first highly solubledinuclear platinum boryl complex, [Pt{B(Br)(tBu)}(μ-Br)(PCy3)]2, could be synthesized with concomitant buildupof the corresponding phosphine-borane adduct. In contrast to thisobservation, reaction of trans-[Pt{B(Br)(Mes)}Br(PCy3)2] with BBr3leads to the formationof the cationic borylene complex trans-[Pt(BMes)Br(PCy3)2] abstraction of the bromo ligandbound mutually transto the boryl ligand in the precursorand concomitant buildup of [BBr4]−. Reactionof [Pt(PCy3)2] with BCl3and subsequentabstraction of the platinum-bound chloro ligand enabled the structuralcharacterization of trans-[Pt(BCl2)(PCy3)2], which is isoelectronic with themetal-only Lewis pair trans-[Pt(BeCl2)(PCy3)2]. The bonding situation in both systems wasinvestigated in detail using quantum chemical calculations. A T-shapedcationic complex, trans-[Pt{B(Br)(Fc)}(PiPr3)2], and its precursor trans-[Pt{B(Br)(Fc)}Br(PiPr3)2], both with reduced steric bulk at the phosphine ligandscompared with their PCy3derivatives, were fully characterized. [ABSTRACT FROM AUTHOR]

New borylene-containing metal-onlyLewis pairs based on group 6metals and ruthenium are prepared by a partially reversible borylenetransfer from group 6 borylene complexes [M{BN(SiMe3)2}(CO)5] (M = Mo, W). The complexescontain strong Ru → Mo/W dative interactions. As in a previousreport on related compounds, redissolving these complexes resultedin reversion back to the precursors, enabled by a sacrificial CO donor.It was observed that this reversion process becomes less selectiveas the group 6 metal becomes heavier, leading to greater amounts ofunidentified byproducts as the group is descended. [ABSTRACT FROM AUTHOR]