Amidinatotetrylenes Donor Functionalized on Both N Atoms: Structures and Coordination Chemistry.

E(hmds)(bqfam) (E = Ge (1a), Sn (1b); hmds = N(SiMe3)2, bqfam = N,N'-bis(quinol-8-yl)formamidinate), which are amidinatotetrylenes equipped with quinol-8-yl fragments on the amidinate N atoms, have been synthesized from the formamidine Hbqfam and Ge(hmds)2 or SnCl(hmds). Both 1a and 1b are fluxional in solution at room temperature, as the E atom oscillates from being attached to the two amidinate N atoms to being chelated by an amidinate N atom and its closest quinolyl N atom (both situations are similarly stable according to density functional theory calculations). The hmds group of 1a and 1b is still reactive and the deprotonation of another equivalent of Hbqfam can be achieved, allowing the formation of the homoleptic derivatives E(bqfam)2 (E = Ge, Sn). The reactions of 1a and 1b with [AuCl(tht)] (tht = tetrahydrothiophene), [PdCl2(MeCN)2], [PtCl2(cod)] (cod = cycloocta-1,5-diene), [Ru3(CO)12] and [Co2(CO)8] have been investigated. The gold(I) complexes [AuCl{κE-E(hmds)(bqfam)}] (E = Ge, Sn) have a monodentate κE-tetrylene ligand and display fluxional behavior in solution the same as that of 1a and 1b. However, the palladium(II) and platinum(II) complexes [MCl{κ3E,N,N'-ECl(hmds)(bqfam)}] (M = Pd, Pt; E = Ge, Sn) contain a κ3E,N,N'-chloridotetryl ligand that arises from the insertion of the tetrylene E atom into an M-Cl bond and the coordination of an amidinate N atom and its closest quinolyl N atom to the metal center. Finally, the binuclear ruthenium(0) and cobalt(0) complexes [Ru2{µE-κ3E,N,N'-E(hmds)(bqfam)}(CO)6] and [Co2{µE-κ3E,N,N'-E(hmds)(bqfam)}(µ-CO)(CO)4] (E = Ge, Sn) have a related κ3E,N,N'-tetrylene ligand that bridges two metal atoms through the E atom. For the κ3E,N,N'-metal complexes, the quinolyl fragment not attached to the metal is pendant in all the germanium compounds but, for the tin derivatives, is attached to (in the Pd and Pt complexes) or may interact with (in the Ru2 and Co2 complexes) the tin atom.

Synthesis and Some Coordination Chemistry of Phosphane-Difunctionalized Bis(amidinato)-Heavier Tetrylenes: A Previously Unknown Class of PEP Tetrylenes (E = Ge and Sn).

The bis(amidinato)-heavier tetrylenes E(bzamP)2 (E = Ge (2a) and Sn (2b); bzamP = N-isopropyl-N'-(diphenylphosphanylethyl)benzamidinate), which are equipped with one heavier tetrylene (germylene or stannylene) and two phosphane fragments (one on each amidinate moiety) as coordinable groups, have been synthesized from the benzamidinum salt [H2bzamP]Cl and GeCl2(dioxane) or SnCl2 in 2:1 mol ratio. A preliminary inspection of their coordination chemistry has shown that their amidinate group can also be involved in the bonding with the metal atoms as tridentate ENP and tetradentate PENP' coordination modes have been observed for the ECl(bzamP)2 ligand of [Ir{κ3E,N,P-ECl(bzamP)2}(cod)] (E = Ge (3a) and Sn (3b); cod = η4-1,5-cyclooctadiene) and the E(bzamP)2 ligand of [Ni{κ4E,N,P,P'-E(bzamP)2}] (E = Ge (4a) and Sn (4b)), which are products of reactions of 2a and 2b with [IrCl(cod)]2 (1:0.5 mol ratio) and [Ni(cod)2] (1:1 mol ratio), respectively. These products contain a 5-membered NCNEM ring that results from the insertion of the metal M atom into an E-N bond of 2a and 2b. Additionally, while iridium(I) complexes 3a and 3b are chloridotetryl derivatives (insertion of the tetrylene E atom into the Ir-Cl bond has also occurred) that have an uncoordinated phosphane group, nickel(0) complexes 4a and 4b contain a tetrylene fragment that, maintaining the lone pair, behaves as a σ-acceptor (Z-type) ligand.

Correction: Fast and scalable solvent-free access to Lappert's heavier tetrylenes E{N(SiMe3)2}2 (E = Ge, Sn, Pb) and ECl{N(SiMe3)2} (E = Ge, Sn).

[This corrects the article DOI: 10.1039/D3SC02709K.].

Fast and scalable solvent-free access to Lappert's heavier tetrylenes E{N(SiMe3)2}2 (E = Ge, Sn, Pb) and ECl{N(SiMe3)2} (E = Ge, Sn).

Iconic Lappert's heavier tetrylenes E{N(SiMe3)2}2 (E = Ge (1), Sn (2), Pb (3)) have been efficiently prepared from GeCl2·(1,4-dioxane), SnCl2 or PbCl2 and Li{N(SiMe3)2} via a completely solvent-free one-pot mechanochemical route followed by sublimation. This fast, high-yielding and scalable approach (2 has been prepared in a 100 mmol scale), which involves a small environmental footprint, represents a remarkable improvement over any synthetic route reported over the last five decades, being a so far rare example of the use of mechanochemistry in the realm of main group chemistry. This solventless route has been successfully extended to the preparation of other heavier tetrylenes, such as ECl{N(SiMe3)2} (E = Ge (4), Sn (5)).

Stannylenes based on pyrrole-phosphane and dipyrromethane-diphosphane scaffolds: syntheses and behavior as precursors to PSnP pincer palladium(II), palladium(0) and gold(I) complexes.

2-Ditertbutylphosphanylmethylpyrrole (H2pyrmPtBu2) and 2,2'-bis(diisopropylphosphanylmethyl)-5,5'-dimethyldipyrromethane ((HpyrmPiPr2)2CMe2) have been used to synthesize new P-donor-stabilized stannylenes in which the Sn atom is attached to one, SnCl(HpyrmPtBu2) (1) and Sn{N(SiMe3)2}(HpyrmPtBu2) (2), or two pyrrolyl-phosphane scaffolds, Sn(HpyrmPtBu2)2 (3), or to a dipyrromethane-diphosphane scaffold, Sn(pyrmPiPr2)2CMe2 (4). It has been found that stannylenes 3 and 4 are excellent precursors to transition metal complexes containing PSnP pincer-type ligands. Their reactions with chlorido transition metal complexes have afforded [PdCl{κ3P,Sn,P-SnCl(HpyrmPtBu2)2}] (6), [PdCl{κ3P,Sn,P-SnCl(pyrmPiPr2)2CMe2}] (7) and [Au{κ3P,Sn,P-SnCl(HpyrmPtBu2)2}] (8), which contain a PSnP pincer-type chloridostannyl ligand. While complexes 6 and 7 are square-planar palladium(II) complexes, compound 8 is an uncommon gold(I) complex having a T-shaped coordination geometry with a very long Sn-Au bond (3.120 Å). The T-shaped palladium(0) complex [Pd{κ3P,Sn,P-Sn(pyrmPiPr2)2CMe2}] (9), which contains an unprecedented PSnP pincer-type stannylene that behaves as a Z-type (σ-acceptor) ligand, has been prepared from 4 and [Pd(η3-C3H5)(η5-C5H5)].