Comparative metallaborane chemistry: preparation and nuclear magnetic resonance studies of some nido-5-metalladecaboranes of rhodium, iridium, ruthenium, and osmium

Polyhedral iridathiaborane chemistry. Reactions of nido-6-SB9H11and of [arachno-6-SB9H12]–with [{Ir(η5-C5Me5)Cl2}2] to give nido-8,7-iridathiaundecarboranes. A nuclear magnetic resonance and structural study

“…The mixture was filtered, the filtrate reduced in volume (rotary evaporator, water-pump pressure, ambient temperature) to ca. 9) 4162( 8) 3836( 8) 1374( 8) 8070(7) 6962( 7) 6592( 7) 7466( 9) 8422( 8) 8764( 8) 6281( 9) 545 1( 10) 7389( 13) 9463( 9) 1584( 8) 2607( 10) 1803( 8) 1479( 8) 2094( 8) 2789( 9) 2620( 9) 3490( 8) 3872( 9) 7416( 12) 8742( 10) 7822( 8) 6727( 8) 6979 ( 10) 1020 pmol) in a solution of [(Ir(q5-C5Me5)C12}2] (200 mg, 250 pmol) in CH,Cl, (ca. 40 cm3) was stirred for 1 h at ambient temperature, during which time the orange colour of the reaction mixture darkened.…”

Polyhedral Oxaruthenaborane Chemistry. Characterisation of a [(η6-C6Me6)RuOB9H13] Species of arachno Eleven-Vertex Cluster Character and Other Aspects of Oxaborane Chemistry

“…The very small quantities permitted only provisional characterisation, but nevertheless we present the results here. Two of the three were tentatively identified as the commo-2-Ru-bi(nido-six-vertex) species [H 10 B 5 RuB 5 H 10 ] 17 (schematic cluster structure XVII) and as [1-(η 6 -C 6 Me 6 )-1-H-arachno-1-RuB 4 H 9 ] 18 (schematic cluster structure XVIII); again these two were simple variants on reported species [31][32][33][34][35][36][37] , allowing their identification by spectroscopic comparison (see Experimental). The remaining compound is proposed to be [4-(η 6 -C 6 Me 6 )-n-arachno-4-RuB 8 H 14 ] 19 of previously unreported nine-vertex metallaborane configuration XIX, isomeric with the previously reported 23 compound [2-(η 6 -C 6 Me 6 )-n-arachno-2-RuB 8 H 14 ] 13 (schematic cluster structure XIII) mentioned above.…”

A simple and high-yield route to iridium, rhodium, osmium and rutheniumnido-6-metalladecaborane compounds

“…The nido-5-metallaborane cluster geometry evident in 7 is known for the following metal fragments: {Fe(1,3,5-Me 3 - 6 -C 6 H 3 )}, 44 , {Co( 5 -Cp)} 45 ,{Rh( 5 -Cp*)} and {Ir( 5 -Cp*)}. 46,47 According to some electron-counting procedures, [22][23][24][25] these transition-element moieties (and others described above that include {Ru(CO)(PPh 3 ) 2 } in 3 and {Os(CO)(PPh 3 ) 2 } in 6) provide two electrons (Number of valence shell electrons on the metal + No. of electrons from ligands -12) to the skeletal bonding of the metalladecaboranes.…”

“…Therefore, the formation of 6 implies a rearrangement of the initial 10-vertex anion or some other intermediate. Given the fact that we have characterized 7 as a nido-5-osamadecaborane, it is reasonable to propose that the nido-6-osmadecaborane anion may undergo a vertex-swing, 47,[66][67][68][69] as illustrated in Scheme 4 C, which transforms the metal centre from a vertex coordinated to three boron units into an osmium centre linked to four boron vertices. This hypothetical nido-5-anion could substitute the chlorine ligands of the platinum complex and liberate a proton to finally form 6, which exhibits the metal centres apart, forming the pentagonal face of the 11-vertex cluster.…”