Salen supported Al–O–CP and Ga–PCO complexes

Abstract

The synthesis and reactivity of salen supported OCP adducts of aluminium and gallium is reported.

Base induced isomerisation of a phosphaethynolato-borane: mechanistic insights into boryl migration and decarbonylation to afford a triplet phosphinidene

“…Selected interatomic distances [Å] and angles [ ]: P1-C1 1.670(2), C1-O1 1.155 (3), C2-P1 1.870(2), C2-B1 1.580(2), C2-N1 1.270(2); P1-C1-O1 173.6(2), C2-P1-C1 96.67(9), B1-C2-P1 122.97(12), B1-C2-N1 120.34(15), P1-C2-N1 116.66 (13). (2), C1-N1 1.195(2), P1-B1 1.912(2); P1-C1-N1 167.50 (13), C1-P1-B1 101.81 (7). structure of 4a ( Fig.…”

“…Young sample tube and a Xenon arc lamp was used, the microwave power was 1 mW and frequency was 9.391 GHz with a modulation amplitude of 1.5 mT. (17), C1-O1 1.239(2), C1-C2 1.407(2), C2-C55 1.449(2), C2-P2 1.7872 (16), P1-B1 1.915(2), O2-B2 1.371(2); B1-P1-P2 108.05 (6), B1-P1-C1 109.32(8), P1-C1-O1 128.70 (13), P1-C1-C2 99.50 (11), O1-C1-C2 131.76 (16), C1-C2-P2 103.95 (11), C1-C2-C55 123.93(15), C2-P2-P1 77.15 (5), C2-P2-O2 103.38 (7), P2-O2-B2 125.73 (11).…”

“…One of the most notable empirical observations from the research carried out thus far concerns the binding preferences of the PCO À ion, revealing that phosphorus-bonded phosphaketenes, [E]-P]C]O, 2 far outnumber their linkage isomers, oxygen-bonded phosphaethynolates, [E]-O-C^P. [3][4][5][6][7] In fact, this latter family of compounds is largely the purview of the s-and f-block elements, and to date, only three structurally authenticated phosphaethynolate compounds have been reported for the elements of the d-and p-blocks. [5][6][7] This is perhaps unsurprising considering that coordination via the oxygen atom, particularly in systems that exhibit a signicant degree of covalency, generates a species with a localised C^P p bond at the expense of a much stronger C]O double bond.…”

“…[3][4][5][6][7] In fact, this latter family of compounds is largely the purview of the s-and f-block elements, and to date, only three structurally authenticated phosphaethynolate compounds have been reported for the elements of the d-and p-blocks. [5][6][7] This is perhaps unsurprising considering that coordination via the oxygen atom, particularly in systems that exhibit a signicant degree of covalency, generates a species with a localised C^P p bond at the expense of a much stronger C]O double bond. Consequently, it is only in highly ionic compounds, or in complexes with strong [E]-O bonds, that bonding via the oxygen atom is observed.…”

Synthesis and decarbonylation chemistry of gallium phosphaketenes

“…5 More recently, Grützmacher and co-workers reported the first examples of aluminium (C) and gallium (D) phosphaethynolate complexes stabilised by salen ligands. 6 The aluminium complex displays O-coordination whilst the gallium analogue was isolated as the P-bound isomer, in keeping with the decreasing oxophilicity upon descending the group, which in turn favours binding via the phosphorus atom. The polydentate character of the salen ligand limits the further reactivity of these species, which behave indistinguishably from one another and in a comparable manner to ionic phosphaethynolate salts of the alkali and alkaline-earth elements.…”