Coordination of acloso-Cluster at Rhodium and Iridium

Abstract

Stanna-closo-dodecaborate [Bu 3 MeN] 2 [SnB 11 H 11 ] reacts as a nucleophile with the rhodium and iridium electrophiles of type [Cp*M(bipy')Cl][BF 4 ] under formation of a transition metal tin bond. The zwitterionic molecules [Cp*M(bipy')(SnB 11 H 11 )] (with M = Rh, Ir) were characterized by NMR spectroscopy, elemental analyses and X-ray crystal structure analyses. A high dipole moment of 25.67 D was calculated by DFT methods in the case of the rhodium derivative. Koordination eines closo-Clusters an Rhodium und Iridium Inhaltsu È bersicht. Der Stanna-closo-dodecaboratcluster [Bu 3 MeN] 2 [SnB 11 H 11 ] reagiert mit den Ûbergangsmetall-elektrophilen [Cp*M(bipy')Cl][BF 4 ] von Rhodium und Iridium unter Bildung einer Zinn±Metall Bindung. Die zwitterionischen Reaktionsprodukte [Cp*M(bipy')(SnB 11 H 11 )] (mit M = Rh, Ir) wurden durch NMR-Spektroskopie, Elementaranalysen sowie Kristallstrukturbestimmungen charakterisiert. Im Fall der Rhodiumverbindung wurde ein Dipolmoment von 25.67 D durch DFT Methoden berechnet.

Cobalt, Rhodium, Iridium, and Ruthenium Carbonyl Complexes with Stanna-closo-dodecaborate:103Rh NMR,119Sn Mössbauer Spectroscopy, and Solid-State119Sn NMR

“…The rhodium–tin distances in complex 1 can be compared with Rh–Sn bond lengths in the literature ,,,,,− Furthermore the heteroborate bridging ligand in compound 1 exhibits a smaller Rh–Sn–Rh bond angle of 60.43° in comparison to the edge-bridging Ph 2 Sn ligand (average 66.95°) in the cluster [Rh 3 (CO) 6 (μ-SnPh 2 ) 3 (SnPh 3 ) 3 ] . Therefore the Rh–Rh bond lengths in this trinuclear cluster (2.91–2.95 Å) are also longer in comparison to the dimer 1 .…”

“…The coordination chemistry of tin is an attractive field of research . Many research goups have synthesized new tin ligands and studied the reactivity and structures of the transition metal tin complexes. − Stannylenes such as bis(dialkylamino)tin or dialkyltin , derivatives are prominent ligands. Novel chelating ligands with two tin donor sites were designed in recent years .…”

“…This complex was protonated even by weak acids and undergoes oxidative addition with hydrogen. Rhodium coordination chemistry with this type of tin ligands was documented in two cases: [Cp*Rh(SnB 11 H 11 )(bipy′)] (bipy′ = 4,4′-di- tert -butyl-2,2′-bipyridine) and [Bu 4 N] 2 [Rh(SnCB 10 H 11 ) 3 - trans -(PPh 3 ) 2 ]. , Further examples of coordination compounds with group(IV)-heteroborate ligands show these ligands in a variety of coordination modes. − …”

Silver Dimer, Tetramer, Polymer, and Network Structures with the Stannylene Stanna-closo-dodecaborate

“…The coordination chemistry of coinage metal electrophiles with heavy main group element ligands often results in the formation of clusters. − The influence of the electronic and steric effects of these main group element ligands on the size of the clusters is still an attractive field of research. We investigated the coordination chemistry of heteroborates and especially of clusters with four element donor sites such as the dianionic stanna- closo -dodecaborate [SnB 11 H 11 ] 2− − and germa- closo -dodecaborate [GeB 11 H 11 ] 2− . In reaction with the metals of the nickel triad we found square-planar and octahedral coordination with the transition metals in formal oxidation state 2 or 4 .…”

Iridium Coordination Compounds of Stanna-closo-dodecaborate

“…It has been well documented that stanna- closo -dodecaborate can act as a versatile ligand with nucleophilic properties in the coordination chemistry of various transition metals . In fact, one iridium coordination compound of the group 14 heteroborate has been established with [Ir(Cp*)(SnB 11 H 11 )(bipy′)] (bipy′ = 4,4′-di- tert -butyl-2,2′-bipyridine, Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl) …”