Advances in the development of complexes that contain a group 13 element chalcogen multiple bond

Abstract

Inorganic group 13 element (M) chalcogenides (E) based on the general formular M2E3 are ubiquitous in synthesis, catalysis and material science. The parent ME fragment which aggregates to form three dimensional networks in the condensed phase can be expected to exhibit multiple bond character between the elements. Low temperature matrix isolation techniques are required to investigate the nature of this elusive species. An alternate approach for respective studies is the synthesis of electron-precise molecular complexes that contain the ME entity and for which isolation at ambient temperature is possible. This is realized by kinetic stabilization with bulky ligands and thermodynamic stabilization using electron donor, as well as acceptor groups attached to the ME functionality (i.e. donor-acceptor stabilization). In this article we revise the literature on complex compounds that exhibit a bonding interaction between a group 13 element atom and a chalcogen atom that is reasonably to be interpreted in terms of a double- or triple bond.

Isoelectronic Aluminium Analogues of Carbonyl and Dioxirane Moieties

“…This is significantly upfield from the shifts observed for IV (250 ppm) and V (À193 ppm), but within the range noted for other [k 2 -Se 2 ] 2À complexes (À408 to 1252 ppm). Previous calculations have also indicated that Al = E multiple bonds contain contribution from zwitterionic resonances (e.g., [Al] + -E À ), [8] which in the case of 2 would involve accumulation of negative charge at selenium. TheW iberg bond index (WBI AlSe = 1.39) is greater than the values calculated for II (WBI AlS = 1.20) [10] and III (WBI AlTe = 1.20), [11] both of which claim to be Al = Edouble bonds.These data indicate the presence of significant multiple-bond character in 2,p articularly when the high degree of polarization in this bond is considered (NBO charges:Al=+1.61, Se = À1.06).…”

“…When carbon is replaced with a X 14 elements in conjunction with one of the chalcogenide elements E (E = O, S, Se,T e), a" heavy" carbonyl group is formed (Scheme 1). [7] Most pertinent to this study are compounds containing the Al=E functional group, [8] which have been isolated for E = O, [9] S, [10] and Te [11] (Figure 1). [7] Most pertinent to this study are compounds containing the Al=E functional group, [8] which have been isolated for E = O, [9] S, [10] and Te [11] (Figure 1).…”

Oxoborane Formation Turns on Formazanate‐Based Photoluminescence

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The synthesis of compounds containing multiple bonds to boron has challenged main-group chemists for decades. C) and as hort BBb ond length of 1.449(3) .C ompounds with boron-chalcogen multiple bonds [5, 6] have been isolated through the combination of strongly donating and sterically bulky ligands, as in compound 3,w hich wasprepared by insertion of elemental Te into aB = Mn bond. We report an oxoborane (B=O) complex that is electronicallys tabilized by af ormazanate ligand in the absence of significant steric bulk and, unlikethe common BX 2 (X = F, Cl) formazanate adducts,e xhibitsi ntense photoluminescence.

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Aluminium‐Mediated Carbon Dioxide Reduction by an Isolated Monoalumoxane Anion

“…TheW iberg bond index (WBI AlO )o f0 .86 is less than predicted for ad ouble bond, and lower than the values calculated for Al=S (WBI AlS = 1.20), [28] Al = Se (WBI AlSe = 1.39), [17d] and Al = Te (WBI AlTe = 1.20). [29] We rationalize this on the basis of al arge contribution from resonance form B (Figure 5), [30] due to the electronegativity difference Dc P {Al/O} = 1.83, [31] which approaches twice the value for Dc P {Al/S} = 0.97 and Dc P {Al/Se} = 0.94. This is further supported by large NPA charges on aluminum (+ 2.03) and oxygen (À1.46), leading us to conclude that the AlÀOb ond may behave chemically as having am ultiple bond character,b ut is dominated by ionic resonance B.…”