Cyclopentadienylidene‐ and Fluoren‐9‐ylidene‐methane‐1,1‐dithiolato Metalates of Tin, Indium and Bismuth

Abstract

Quaternary ammonium and phosphonium stannates(II), indates(III) and bismuthates(III) displaying dianionic S,S dithiolate chelate ligands [CpCS2]2− and [FluoCS2]2− (Cp=C5H4, Fluo=C13H8) are described. With Sn(II) as central template ion, homoleptic metalates Cat2[Sn(CpCS2)2], with In(III) and Bi(III), highly charged Cat3[In(CpCS2)3] and Cat3[Bi(CpCS2)3] were obtained. A complementary series was characterized for fluoren‐9‐ylidene‐derived metalates Cat2[(FluoCS2)2Sn], Cat3[(FluoCS2)3In] and Cat3[Bi(FluoCS2)3]. Heteroleptic indate(III) NBu4[CpCS2InMe2] (3‐NBu4) and homoleptic [PPh4]3[In(CpCS2)3] (6‐PPh4) as well as stannates(II) [PPh4]2[Sn(CpCS2)2] (5‐PPh4) and [NBu4]2[Sn(FluoCS2)2] (9‐NBu4) were XRD structurally characterized. Reaction of electron‐rich ligand Na2(FluoCS2) with SnCl4 did not lead to an expected stannate(IV) but to a redox reaction and metal free 3,5‐di(9H‐fluorene‐9‐ylidene)‐1,2,4‐trithiolane (12), which was characterized by XRD analysis. The title compounds are related to much better investigated dithiocarbamato(2‐) complexes, well‐established precursors for thermal metal sulfide depositions. In this respect, an explorative DSC‐TGA measurement following the thermal decay of [PPh4]3[(CpCS2)3In] (6‐PPh4) revealed the formation of β‐In2S3 at relatively high temperatures, proven by PXRD.

Dihydroguaiazulenide Complexes and Catalysts of Group 8–12 Transition Metals: Ligands from Renewable Feedstock Replace, even Outmatch Petrochemical Based Cyclopentadienyl Chemistry

“…A neutral Gua ligand complex of type [Rh(Gua)(cod)]BF 4 was reported to act as catalyst at 2 mol % load in the insertion of dimethyl acetylenedicarboxylate into the 5-membered ring of Gua forming heptalene-1,2-dicarboxylate. [57] So far, there are no reports of using isomerically pure 2H-guaiazulenide (GuaH) anion complexes, now accessible via a catalytic hydrolithiation of Gua, [22] for catalysis studies. We were inspired, as volatile complexes [Cp R PtMe 3 ] (R=H, Me) [10,40,41] are known to be important precatalysts in silicone rubber industry.…”

“…[46] Due to strong covalent PtÀ C bonding interactions, the C4-C10-C9-C8 torsion angle is less distorted from planarity (2.4°) compared to the ionic potassium salt (8-H-GuaH)K(18-C-6) (7.7°). [22] Group 11 and 12 complexes Finally, we present two examples of d 10 complexes decorated by the GuaH ligand. Following reports of the synthesis of [(η 5 -C 5 H 5 )Cu(PPh 3 )] by Cotton et al [47] and Zybill et al, [48] we reacted [Cu(PPh 3 )Cl] 4 [49] with equimolar amounts (per Cu atom) of 1 a. Cuprated carbanion complex 11 formed in almost quantitative yield (Scheme 6).…”

“…In our previous paper [22] we reported the discovery of a rather uncommon catalytic hydrolithiation method, applied to natural product guaiazulene. Formal addition of LiH to a polar olefinic bond led to the previously unmanaged isolation of analytically and isomerically pure, storable cyclopentadienide carbanion synthon (8-H-GuaH)Li (Scheme 1).…”

Calix[4]pyrrolato Stannate(II): A Tetraamido Tin(II) Dianion and Strong Metal‐Centered σ‐Donor

“…[9] We surmised that the coordination of a fourth anionic ligand to Sn II might push the σ‐donor strength even farther. Sn II ‐based dianions are scarce, [10] and molecular compounds are limited to [F] 2− [11] and [G] 2− , [12] which are stabilized by charge delocalization into the carborate ( [F] 2− ) or the fluorenyl moiety ( [G] 2− ). Given the substantial π‐donor ability of nitrogen and the unique role of amido substituents in low valent tin chemistry, [13] the formation of a yet elusive tetraamido Sn II dianion, [Sn(NR 2 ) 4 ] 2− , appeared of particular relevance.…”

Calix[4]pyrrolatostannat(II): Ein Tetraamidozinn(II)dianion als starker, metallzentrierter σ‐Donor

“…[8] Wir vermuteten, dass die Koordination eines vierten anionischen Liganden an Sn II die σ-Donorstärke noch weiter steigern könnte. Dianionen auf Zinn(II)basis sind rar, [9] und molekulare Verbindungen beschränken sich auf [F] 2À [10] und [G] 2À , [11] welche durch Ladungsdelokalisierung im Carborat ([F] 2À ) oder Fluorenylgruppe ([G] 2À ) stabilisiert werden.…”