Abstract
The novel phosphanylalumanes, Al–P single-bond species, fully bearing carbon protecting groups on aluminum and phosphorus atoms, are synthesized by the reactions of aluminum monohalides [(t-Bu)2AlBr and (C6F5)2AlCl·0.5(toluene)] with Mes2PLi. Regarding the t-Bu system, λ3,λ3-phosphanylalumane is obtained. Concerning the C6F5 system, on the other hand, the corresponding LiCl complex, λ4,λ4-phosphanylalumane, is obtained. The Al–P bond lengths of C6F5-substituted λ3,λ4-, and λ4,λ4-derivatives are much shorter than those of the reported λ3,λ4-phosphanylalumane derivatives and comparable to that observed for the previously reported λ3,λ3-phosphanylalumanes. Theoretical calculations reveal that the binding of the C6F5 groups to Al results in a large contribution of Al and a large s-character in the Al–P bond of phosphanylalumanes. Considering t-Bu-substituted phosphanylalumanes, the Al–P bond lengths reflect the coordination number of Al, showing a longer Al–P bond length in the case of λ4-Al as compared with that of λ3-Al. Combining the structural, spectroscopic, and theoretical results, the t-Bu-substituted λ3,λ3-phosphanylalumane has well separated vacant p orbital and lone pairs, which is suitable for reactivity studies.
Highlights
The bonding between group 13 (E) and group 15 (Pn) elements formulated as R2 E–PnR2 have attracted much attention due to their relationship, including the vacant p orbital on E and the lone-pair electrons on Pn
The calculated Al–P bond length of 2 almost was similar to or for λ,λ -phosphanylalumane 1 displayed a resonance at δ = −111.7 ppm that is the most upfield slightly shorter than that of 1 (1: 2.348 Å vs. 2: 2.322 Å)
These results indicated that the C6F5 groups among those of the synthesized phosphanylalumane derivatives (1·(t-BuNC): −96.7 ppm, 2·Et2 O: greatly affected the Al–P bond regardless of the coordination number to the Al center, the reasons of
Summary
The bonding between group 13 (E) and group 15 (Pn) elements formulated as R2 E–PnR2 have attracted much attention due to their relationship, including the vacant p orbital on E and the lone-pair electrons on Pn. The heavier analogues, λ3 ,λ3 -phosphanylalumanes (R2 Al–PR2 ), decrease the π-type interaction between the E and Pn atoms compared to those of aminoboranes [2,3,4] and phosphanylboranes [5,6] due to the longer E–Pn σ-bond. Inorganics 2019, 7, 132 are reactive substituents (H or a halogen atom) on P or Al moiety, another aluminum or phosphorus reagents react to give a λ3,λ3-diphosphanyl-λ3-alumane [16] and λ3-phosphanyl-λ3,λ3-dialumane [17],. Groups we report thealuminum synthesis and of λphosphorus which are fully on by the aluminum, we groups chose t-Bu
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