Abstract
Reaction of [Ru(PPh 3) 4H 2] with BH 3 · thf at room temperature gives borane oligomerisation with the formation of the 6-vertex metallaborane nido-2-[Ru(PPh 3) 2(H)B 5H 10] ( 1). This cluster is also formed by reaction of [Ru(PPh 3) 4H 2] with nido-B 5H 9. Compound ( 1) is readily deprotonated by KH in thf at the unique basal B–H–B bridge to give nido - 2 - [ Ru ( PPh 3 ) 2 ( H ) B 5 H 9 - ] [ K + ] ( 2). In contrast to [Ru(PPh 3) 4H 2] reaction of [ cis-Ru(PMe 3) 4H 2] with BH 3 · thf gives initially the known borohydride [Ru(PMe 3) 3(H)(η 2-BH 4)] which reacts with excess BH 3 · thf to give the 5-vertex metallaborane nido-2-[Ru(PMe 3) 3B 4H 8] ( 3). Reaction of [ cis-Ru(PMe 3) 4H 2] with nido-B 5H 9 also gives ( 3) and nido-2-[Ru(PMe 3) 3B 9H 13] ( 4). [ cis-Ru(PMe 3) 4H 2] is conveniently prepared in high yield in a one-pot synthesis by the sodium amalgam reduction of RuCl 3 · 3H 2O in thf with excess PMe 3 under dinitrogen.
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