Heavier group 13/15 multiple bond systems: synthesis, structure and chemical bond activation

Abstract

Heavier group 13/15 multiple bonds have been under investigation since the late 80s and to date, several examples have been published, which shows the obsoleteness of the so-called double bond...

Carbon–chalcogen bond formation initiated by [Al(NONDipp)(E)]−anions containing Al–E{16} (E{16} = S, Se) multiple bonds

“…This is accompanied by an increase in the bond ellipticity, 3, from 0.033 in [1-O] À to 0.139 in [1-Te] À , indicating a greater p-character of the Al-E{16} bond in the order O < S < Se < Te, consistent with the WBI analysis. 61,62 Reactivity of K[Al(NON Dipp )(E)] (E ¼ S, Se) Reactions with 13 CO 2 . The room temperature reaction of K[1-S] with 13 q(Al) ¼ +1.93, q(O) ¼ À1.23 The aluminium atoms are distorted tetrahedral with the thiocarbonate ligand dening the smallest angle (76.50 (7) and 76.61(8) at Al1 and Al2, respectively).…”

“…61,62 Reactivity of K[Al(NON Dipp )(E)] (E ¼ S, Se) Reactions with 13 CO 2 . The room temperature reaction of K[1-S] with 13 q(Al) ¼ +1.93, q(O) ¼ À1.23 The aluminium atoms are distorted tetrahedral with the thiocarbonate ligand dening the smallest angle (76.50 (7) and 76.61(8) at Al1 and Al2, respectively). The Al-S bond lengths (2.2842(10) A and 2.2812(11) A) are considerably longer than in K[1-S] and [K(2.2.2)crypt][1-S], and are consistent with sum of the molecular covalent single bond radii, r 1 (S(r 1 ) ¼ 2.29 A).…”

“…[9][10][11] More recently, well dened examples of Al-E{n} multiple bonds have been recorded with elements from groups n ¼ 13, 15 and 16. 12,13 For Al-E{13} multiple bonds, examples of charged species containing homometallic dialuminium compounds (E {13} ¼ Al), with an Al-Al bond order >1 have been known for almost 30 years. [14][15][16][17] This pioneering work was complimented by examples of neutral compounds of 'masked' dialumenes that were isolated as the products of cycloaddition with aromatic solvents.…”

Structural Snapshots in Reversible Phosphinidene Transfer: Synthetic, Structural, and Reaction Chemistry of a Sn═P Double Bond

“…Yoshifuji’s synthesis of a stable diphosphene and West’s synthesis of tetramesityldisilene, both in 1981, did much to repudiate the so-called “double bond rule” and the implied limit on multiple bonding between heavier main group elements . Since these landmark reports, both homo- and heteronuclear multiple bonds featuring elements from groups 14–16 have attracted enormous interest . With respect to E 14 –E 15 multiple bonds, the initial report of a phosphaalkyne RCP, was followed by the isolation of a range of phosphaalkenes .…”

Deoxygenation of chalcogen oxides EO2 (E = S, Se) with phosphaWittig reagents

“…We have demonstrated the facile NH- 48 as well as OH-bond 49 activation at the P(I) center as well as the cleavage of the terminal C(sp 2 )−H bonds of NHOs to give P-substituted NHOs. 50 Utilizing phospha-and arsa-Wittig reagents as pnictinidene transfer reagents, phospha-as well as arsaalumenes 51 -compounds showing E 13 -E 15 multiple bonding 52 -could be generated in the reaction with (Cp*Al)4 (Scheme 2). Overall, quite a remarkable portfolio of phosphanylidenephosphorane chemistry was established in the last few years.…”