Modulating the frontier orbitals of L(X)Ga-substituted diphosphenes [L(X)GaP]₂(X = Cl, Br) and their facile oxidation to radical cations

Abstract

Modulating the electronic structures of main group element compounds is crucial to control their chemical reactivity. Herein we report on the synthesis, frontier orbital modulation, and one-electron oxidation of two...

Syntheses and Structures of 5‐Membered Heterocycles Featuring 1,2‐Diphospha‐1,3‐Butadiene and Its Radical Anion

“…2 crystallizes in the monoclinic space group P 2 1 / n with one independent molecule and disordered solvent molecule ( n ‐hexane) in the asymmetric unit [17] . The short P1−P2 (2.0662(5) Å) and C30−C31 (1.399(2) Å) bonds within the planar P 2 C 2 π‐conjugated unit are comparable to other P−P and C−C double bonds [1d,e,8,15] and calculated values [18a] . The P2−C30 (1.7919(14) Å) bond length is also consistent with the sum of the calculated single bond radii (P 1.11 Å; C 0.75 Å), [18b] and the Ga1−P1 (2.2844(4) Å) and C31−N3 (1.3815(18) Å) bond lengths of 2 agree with experimental Ga−P [14,15] and C−N [1,8–10] single bonds, respectively.…”

“…We recently showed that electropositive L(X)Ga substituents stabilize open‐shell and π‐bonded pnictogen compounds [11] and other unusual bonding situations [12] . Moreover, gallaphosphenes [13] were found to undergo cycloaddition and E−H (E = N, O, S, Se) bond activation reactions, [13,14] and carbene‐coordinated diphosphenes were oxidized to radical cations [15] . We report here the synthesis of LGa(P 2 OC)cAAC 2 (L = HC[C(Me)N(Ar)] 2 ; Ar = 2,6‐ i‐ Pr 2 C 6 H 3 ) with a 1,2‐diphospha‐1,3‐butadiene moiety, its radical anion 3 ⋅ − and the 1,2‐diphospha‐1,3‐butadiene anion 4 − .…”

Syntheses and Structures of 5‐Membered Heterocycles Featuring 1,2‐Diphospha‐1,3‐Butadiene and Its Radical Anion

“…2 crystallizes in the monoclinic space group P 2 1 / n with one independent molecule and disordered solvent molecule ( n ‐hexane) in the asymmetric unit [17] . The short P1−P2 (2.0662(5) Å) and C30−C31 (1.399(2) Å) bonds within the planar P 2 C 2 π‐conjugated unit are comparable to other P−P and C−C double bonds [1d,e,8,15] and calculated values [18a] . The P2−C30 (1.7919(14) Å) bond length is also consistent with the sum of the calculated single bond radii (P 1.11 Å; C 0.75 Å), [18b] and the Ga1−P1 (2.2844(4) Å) and C31−N3 (1.3815(18) Å) bond lengths of 2 agree with experimental Ga−P [14,15] and C−N [1,8–10] single bonds, respectively.…”

“…The short P1−P2 (2.0662(5) Å) and C30−C31 (1.399(2) Å) bonds within the planar P 2 C 2 π‐conjugated unit are comparable to other P−P and C−C double bonds [1d,e,8,15] and calculated values [18a] . The P2−C30 (1.7919(14) Å) bond length is also consistent with the sum of the calculated single bond radii (P 1.11 Å; C 0.75 Å), [18b] and the Ga1−P1 (2.2844(4) Å) and C31−N3 (1.3815(18) Å) bond lengths of 2 agree with experimental Ga−P [14,15] and C−N [1,8–10] single bonds, respectively. The five‐membered GaP 2 OC heterocycle is coplanar with the P 2 C 2 π‐conjugated system, and the C 3 N 2 Ga metallacycle is perpendicular to this plane.…”

An Isolable Heteroleptic Diarylphosphinyl Radical

“…Phosphorus-centered radicals are an important class of reactive intermediates that are involved in many chemical reactions . During the past decades, a variety of stable phosphorus-centered neutral, cationic, and anionic radicals have been isolated and structurally characterized. However, the isolation of stable phosphinyl [R 2 P] • radicals is still quite challenging due to their intrinsic high propensity to dimerize.…”