Intermediates and products of the reaction of Zn(ii) organyls with tetrel elementZintlions: cluster extensionversuscomplexation

Abstract

Upon reactions of Zintl ions with Zn(ii) organyls various Zn-Zintl clusters as well as Zn-amide intermediates were isolated.

σ‐Aromaticity‐Induced Stabilization of Heterometallic Supertetrahedral Clusters [Zn6Ge16]4− and [Cd6Ge16]4−

“…There is precedent for such geometries in metal ions with a d 10 configuration, such as [η 2 :η 2 ‐(Sb 2 Sn 2 )Au I (Sb 2 Sn 2 )] 3− , but approximately tetrahedral coordination is a norm for d 10 ions, as for example in [η 2 :η 2 ‐Sn 4 Au I Sn 4 ] 7− and other analogues . The three Ge‐Ge bonds of the coordinated edges of the Ge 4 units (2.709–2.717 Å in 1 a , 2.721–2.752 Å in 2 a ) are elongated substantially compared to those in the isolated [Ge 4 ] 4− anion (2.574–2.587 Å), while the three non‐coordinated Ge‐Ge bonds in each Ge 4 unit are, conversely, slightly shorter than those in [Ge 4 ] 4− and other Zn/Ge clusters . The structure of 1 a can usefully be compared to the [(Ge 4 )Zn(Ge 4 )] 6− anion, which is found in two distinct isomeric forms in Cs 6 ZnGe 8 and K 14 ZnGe 16 , where the two Ge 4 units are coordinated η 3 :η 3 and η 3 :η 2 , respectively .…”

Assembly of One to Four As4 Analogues, (Ge2As2)2− or (Ge3As)3−, in the Coordination Sphere of [PhM]+, [MesM]+, or M2+ (M=Zn, Cd, Hg)

“…Such clusters were obtained by solid state reactions of the elements instead (right), hence in the Zintl phases A 14 ZnGe 16 (A=K, Rb) [7c] or Cs 6 Ge 8 Zn, [4] as the very high charge density requires the close proximity of alkali metal ions—and not the bulky [A(cypt‐222)] + complexes with their comparably low charge density. Noteworthy however, a related complex with a protonated {Ge 4 } unit, [{η 2 ‐(HGe 4 )}ZnPh 2 ] 3− , was obtained from the reaction of the extraction solution of K 6 Rb 6 Ge 17 in en/crypt‐222 with [ZnPh 2 ] [18] . This indicates some flexibility of the reaction space including homoatomic units, too, by protonation.…”

“…Noteworthy however, a related complex with a protonated {Ge 4 } unit, [{η 2 -(HGe 4 )}ZnPh 2 ] 3À , was obtained from the reaction of the extraction solution of K 6 Rb 6 Ge 17 in en/crypt-222 with [ZnPh 2 ]. [18] This indicates some flexibility of the reaction space including homoatomic units, too, by protonation.…”

Capture the missing: formation of (PbBi3)− and {[AuPb5Bi3]2}4− via atom exchange or reorganization of the pseudo‐tetrahedral Zintl anion (Pb2Bi2)2−

“…Upon introducing d‐block metal atoms, Tt 4 4− anions usually maintain their overall intact tetrahedral form in the resulting complexes, such as in [(MesCu) 2 (η 3 :η 3 ‐Tt 4 )] 4− (Tt = Si, Ge), [(EtZn) 2 (η 3 :η 3 ‐Ge 4 )] 2− , and [(η 2 ‐Sn 4 )Zn(η 3 ‐Sn 4 )] 6− 13–16 . This concept can also be extended to p‐block element atoms linking the tetrahedral units, which is exemplified by [In(η 3 ‐Pb 4 ) 2 ] 5− in the A 5 InPb 8 (A = K, Rb) alloy 17 …”

“…1 Upon introducing d-block metal atoms, Tt 4 4− anions usually maintain their overall intact tetrahedral form in the resulting complexes, such as in [(MesCu) 2 (η 3 :η 3 -Tt 4 )] 4− (Tt = Si, Ge), [(EtZn) 2 (η 3 :η 3 -Ge 4 )] 2− , and [(η 2 -Sn 4 )Zn(η 3 -Sn 4 )] 6− . [13][14][15][16] This concept can also be extended to p-block element atoms linking the tetrahedral units, which is exemplified by [In(η 3 -Pb 4 ) 2 ] 5− in the A 5 InPb 8 (A = K, Rb) alloy. 17 It was shown that (Ge 2 Pn 2 ) 2− anions (Pn = P, As) undergo atom exchange reactions in solution according to Equation (1), thereby form-ing the new species (Ge 3 Pn) 3− and (GePn 3 ) − in situ in relatively high yield.…”