Structural diversity of mixed polypnictogen complexes: dicationic E₂E′₂ (E ≠ E′ = P, As, Sb, Bi) chains, cycles and cages stabilized by transition metals

Abstract

The reactivity of the tetrahedral dipnictogen complexes [{CpMo(CO)2}2(µ,η2:η2-EE')] (E, E' = P, As, Sb, Bi; "Mo2EE'") towards different one-electron oxidation agents is reported. Oxidation with [Thia][TEF] (Thia+ = C12H8S2+; TEF−...

Heavy Chains: Synthesis, Reactivity and Decomposition of Interpnictogen Chains with Terminal Diaryl Bismuth Fragments

“…The Bi−As bond lengths are 273.6(1) and 275.1(1) pm. Again, this fits well to other described covalent Bi−As single bonds (264(2)–283.77(1) pm)[ 3 , 5 , 13 , 24 , 25 ] The Bi−As−Bi angle is 90.97(4)°, which is in a similar range than the Bi−P−Bi angle in 1 Ph . The Bi−Bi distance (391.2(1) pm) is smaller than the sum of van der Waals radii (414 pm) [23] but larger than in 1 Ph (373.61(6) pm).…”

“…Despite the large t Bu and P t Bu 2 substituents at the arsenic atom, the Bi−As distance of 271.91(4) pm is on the shorter end of Bi−As single bonds. Nonetheless, it fits well to 2 Ph , 2 Mes , 3 Ph and other compounds described in the literature (271.7(9)–282.61(1) pm) [3,5,13,24,25] . With 236.0(1) pm, the As−P distance is similar to compound 4 Ph (235.40(7) pm).…”

“…19(3) pm in 3 Ph , is slightly shorter than in compound 2 Ph but still fits well to the other described BiÀ As bonds. [3,5,13,24,25] The AsÀ As bond length of 243.42 (6) pm is similar to model compounds like (tBuAs) 4 (244.2(1)-244.4(1) pm) [26] or the before mentioned ((Me 3 Si) 2 CH)ClBi) 2 As) 2 (245.0(3) pm). [3] Looking along the AsÀ As axis, the two diphenylbismuthanyl Chemistry-A European Journal fragments are almost in an ecliptic arrangement with a BiÀ AsÀ AsÀ Bi torsion angle of 29.81(2)°.…”

“…A Bi−As−As−Bi motive can only be found in one other literature known compound, (Cl(SiMe 3 ) 2 CHBi) 2 As) 2 , where an As 2 fragment is bound to four bismuth atoms [3] . The Bi−As bond length of 272.19(3) pm in 3 Ph , is slightly shorter than in compound 2 Ph but still fits well to the other described Bi−As bonds [3,5,13,24,25] . The As−As bond length of 243.42(6) pm is similar to model compounds like ( t BuAs) 4 (244.2(1)–244.4(1) pm) [26] or the before mentioned ((Me 3 Si) 2 CH)ClBi) 2 As) 2 (245.0(3) pm) [3] .…”

The Pnictogen Bond: The Covalently Bound Arsenic Atom in Molecular Entities in Crystals as a Pnictogen Bond Donor

“…While inspecting all these results, we found all As···Cl contacts to be a genuine contact, yet many are missing because of the constraint imposed on the bond distance range. For example, the crystal ([C 16 AlCl 12 F 24 O 4 ][C 14 H 10 AsBiMo 2 O 4 ](CH 2 Cl 2 ) 0.5 (CSD ref: CALFAA [ 142 ]) contains an As···Cl interaction at a distance of 4.136 Å and an Mo–As···Cl bond angle of 179.9°. We then extended the bond distance range to 2.6–4.3 Å with the same angular range as the constraint of our search; this produced 244 results with 496 close contacts.…”