Metalation of tBu 2 PH(BH 3 ) (1H), iPr 2 PH(BH 3 ) (2H), iPrPhPH(BH 3 ) (3H), Ph 2 PH(BH 3 ) (4H) or (Mes) 2 PH(BH 3 ) (5H) with one equivalent of nBuLi in either diethyl ether or THF gave the corresponding phosphido-borane complexes, which were obtained as single crystals of the solvates [{tBu 2 P(BH 3 )}Li, and [{(Mes) 2 P(BH 3 )}Li(THF) 2 ] 2 (5Li) after crystallization from diethyl ether; the alternative adduct [{Ph 2 P(BH 3 )} Li(TMEDA)] ∞ (4Li(TMEDA)) was isolated from the reaction of 4Li with TMEDA. Similar metalation reactions between 1H, 2H or 4H and PhCH 2 Na gave the complexes [{tBu 2 P(BH 3 )}Na(THF)] ∞ (1Na) and [{iPr 2 P(BH 3 )}Na(THF)] ∞ (2Na), and [{Ph 2 P(BH 3 )}Na-(TMEDA)(THF)] ∞ (4Na(TMEDA)). Compounds 1Li, 2Li, 3Li, 4Li and 4Li(TMEDA) crystallize as zig-zag polymers, while 5Li crystallizes as a centrosymmetric dimer; compounds 1Na and 2Na crystallize as ribbon polymers, although these differ significantly in structure, while 4Na(TMEDA) crystallizes as a zig-zag polymer.

The reactions between SnCl2 and three equivalents of the alkali metal phosphido-borane complexes [R2P(BH3)]M yield the corresponding tris(phosphido-borane)stannate complexes [LnM{R2P(BH3)}3Sn] [R2 = iPr2, LnM = (THF)3Li (2Li), (Et2O)Na (2Na), (Et2O)K...