Würfelspiele im Bereich der Heterokubane: Synthese und Charakterisierung von Molekülverbindungen der Systeme Sn/E und Pb/E (E = P/As)

Abstract

The heterocubane-like molecules [tBu 2 PhSiESn] 4 (E = P (2), As (3)) and [(Me 3 Si) 3 SiPM] 4 (M = Sn (4), Pb (5)) were obtained by the reaction of primary silyl phosphines or -arsines with M{N(SiMe 3 ) 2 } 2 . Likewise, the reactions of the miscellaneously substituted arsine (Me 3 Si) 3 SiAs(SiMe 3 ) 2 (1) with MCl 2 yielded the heterocu-

Low‐Valent Group 14 Phosphinidenide Complexes [({SIDipp}P)2M] Exhibit P–M pπ–pπ Interaction (M=Ge, Sn, Pb)

“…[(Pb(m-PtBu 2 )PtBu 2 ] 2 278.1(4)-281.2(3) pm; [40] [Pb(P(SiMe 3 ) 2 ) 2 ] 2 269.6(7)-279.6(7) pm; [57] [(Me 3 Si) 3 SiPPb] 4 271.5(1)-274.1(1) pm [38] ). Compounds that exhibit a comparable arrangement of ligands towards the central P 2 Pb 2 cycle are the phosphanylhaloplumbylene [Fe(C 5 H 4 PtBu) 2 (PbX) 2 ] with X = Cl, Br, Mes) descripted by Pietschnig.…”

“…Compound 5 exhibits notably shorter PÀPb distances (258.0(3)-258.2(3) pm) than found in [{(Tripp)(tBu)(F)-Si}(iPr 3 Si)P] 2 Pb (265.4(4) pm), which clearly provides the assumption of a higher bond order. [37] Other literature-known compounds containing threefold exclusively phosphorus coordinated lead atoms show even longer PÀPb distances ([K(SI-MesP) 3 Pb]: 274.5 (19)-278.3 (18) pm; [2] [PbPR] 4 with R = SitBu 2 Ph: 271.1(4)-274.6(4) pm; [38] for R = Si(SiMe 3 ): 271.5(1)-274.1(1) pm [39] or [Pb(m-PtBu 2 )PtBu] 2 : 278.1(4)-281.2(3) pm [40] ). The P-Pb-P angle (84.6(1)8) is slightly sharper than in 3 or 4 and but significantly sharper than in [{(Tripp)(tBu)(F)-Si}(iPr 3 Si)P] 2 Pb (97.88(4)8), [37] which is assigned to the steric strain exerted by the large substituents.…”

Low‐Valent Group 14 NHC‐Stabilized Phosphinidenide ate Complexes and NHC‐Stabilized K/P‐Clusters

“…ÀSn:2 64.6(4)-267.3(5) pm;R = Si(SiMe 3 ) 3 or Si-tBu 2 Ph].I na ll these compounds,t he tina toms are threefoldcoordinated exclusivelyb yp hosphorus [25,26]. The PbÀPb ond length [274.5(19)-278.3(18) pm] of 4 is in good accordance with corresponding lengths in other compounds described in the literature containing threefold exclusively phosphorus-coordinated lead atoms, such as [PbPR] 4 [for R = SitBu…”

Cage Compounds of Phosphorus and the Heavier Group 14 Elements

“…[Sn{SnN(SiMe 3 ) 2 } 2 { i Pr 2 SiPMe) 2 } 2 ] represents another more open structured compound 10. The compounds 3 and 4 are the first examples of Pb/P cage compounds of type B and C , whereas only recently the first type A compounds of lead have been published 11. The lead cage compound 4 completes the row of the known hexameric tin and germanium derivatives [Sn 6 (PSi i Pr 3 ) 6 ] and [Ge 6 (PSi i Pr 3 ) 6 ]of type B , while 3 represents the lead congener of the tin compounds [Sn 7 (PSi i Pr 3 ) 7 ]7 and [Sn 7 (PR) 7 ] ( R = t Bu, cyclohexyl, 1‐adamantyl)12 of type C .…”