With the chelating aminophosphane ligands Ph2P-(o-C6H4)-N(CH3)2 (PNMe2) and Ph2P-(o-C6H4)-NC4H8 (PNpy), four halide (Cl, Br, I)-bridged copper coordination compounds [Cu(μ-Cl)(PNMe2)]2 (1), [Cu(μ-Br)(PNMe2)]2 (2), [Cu(μ-I)(PNMe2)]2 (3), [Cu(μ-I)(PNpy)]2 (4) were synthesized structurally characterized. Their photophysical properties studied in detail. The complexes exhibit strong blue (λmax = 464 (3) 465 nm (4)) green 506 (1) 490 (2)) luminescence as powders with quantum yields of up to 65%...

Abstract Intramolecular germylene, stannylene, and plumbylene Lewis pairs were reacted with hexanal yielded the cyclic addition products only germanium tin reagents. In further reactivity studies, hydroboration of aldehydes ketones catalyzed by intramolecular was studied. case germylene pair, product oxidative pinacolborane at moiety observed. According to stoichiometric as well catalytic experiments, pair acts a catalyst in ketones. The homologous stannylene forms reactive hydride during...

<italic>N</italic>-Heterocyclic carbenes are shown to cleanly abstract dihydrogen from organotin di- and trihydrides intermediately form the reactive stannylene species [R₂Sn] [R′SnH], respectively, which undergo further reactions.

Abstract A series of benzyl(diphenylphosphino) and o ‐phenyl(diphenlyphosphino) substituted germylenes plumbylenes were synthesized by nucleophilic substitution between the respective lithium reagent tetrylene halide. The Lewis pairs characterized X‐ray crystallography NMR spectroscopy. reactivity tetrylenes was investigated with respect to azide addition. In germylene case, germaniumimide formed as kinetically controlled product, which rearranges upon heating give phosphinimide. stannylene...

Although hydrides of the group 14 elements are well-known as versatile starting materials in many chemical transformations, a hydride lead oxidation state II is so far unknown. In this work, we finally complete jigsaw puzzle by reporting isolation first low valent organolead hydride. The thermolabile dimeric was synthesized at temperature and features 1H NMR signal (in solution 35.61 ppm; solid 31.1 ppm) lowest field observed for diamagnetic compound agreement with quantum predictions.

Bermuda triangle: The first molecule containing a cyclic three-membered SnCP ring has been synthesized and characterized. This SnIIP Lewis pair reacts at room temperature with alkynes pentene to give the five-membered addition products. In case of pentene, this reaction is reversible temperature. Trip=2,4,6-iPr3C6H2. As service our authors readers, journal provides supporting information supplied by authors. Such materials are peer reviewed may be re-organized for online delivery, but not...

Intramolecular stannylene-based Lewis pairs with phosphine bases were synthesized at the ortho position in benzene or peri acenaphthene. The spectroscopic data of are discussed, and reactivity toward unsaturated hydrocarbons organic azides is presented.

Since their first description over a decade ago, organotin(ii) hydrides have been an iconic class of compounds in molecular main group chemistry. Among other approaches they accessed from the hydrogenation distannynes. We herein report accessibility direction by dehydrogenation organotin trihydride. On reacting pyridine and amine bases with bulky substituted trihydride Ar*SnH3 (Ar* = 2,6-trip2(C6H3)-, trip 2,4,6-triisopropylphenyl) hydrogen evolution was observed. In case catalytic amounts...

Tetrylidynes [(Me

The coordination chemistry of cyclic stannylene-based intramolecular Lewis pairs is presented. P→Sn adducts were treated with [Ni(COD)2] and [Pd(PCy3)2] (COD = 1,5-cyclooctadiene, PCy3 tricyclohexylphosphine). In the isolated compounds stannylene moiety acts either as an acceptor or a donor ligand. Examples dynamic switch between these two modes P-Sn ligand are illustrated structures in solid state together heteronuclear NMR spectroscopic findings discussed. case Ni(0) complex, (119)Sn...

Abstract Alkyltin trihydride [(Me 3 Si) 2 CHSnH ] was synthesized and the reductive elimination of hydrogen from this species investigated. A methyl‐substituted N‐heterocyclic carbene reacts with organotrihydride in dependence on stoichiometry solvent to give a series products dehydrogenative tin–tin bond formation. Besides characterization adduct alkyltin(II) hydride, Sn 4 chain also isolated, encompassing two stannyl–stannylene sites, which are stabilized each as NHC‐adducts. Complete...

Hydrogen can be selectively removed from organotin trihydrides to generate the corresponding organohydrostannylene intermediates. Depending on size of substituent and mode generation, intermediates undergo further reactions. Herein, we report formation a variety hydrides with tin in oxidation states Sn(II) , Sn(I) -Sn(III) Sn(III) all accessed by controlled removal hydrogen tetravalent Ar'Sn(IV) trihydride (Ar'=2,6-dimesitylphenyl, mesityl=2,4,6-trimethylphenyl).

An intramolecular germylene-phosphine Lewis pair (1) was reacted with germanium dichloride to give in 92% yield a phosphine adduct of chloro substituted germyl-germylene (2). After reduction this strong reductants like the Mg(I) reagent {(MesNacnac)Mg}2 (72% yield) or Na (52% stabilized digermavinylidene (3) isolated as crystalline material [MesNacnac = {[(Mes)NC(Me)]2CH}-, Mes 2,4,6-Me3C6H2]. The electronic structure investigated by density functional theory calculations. In reaction...

Reactions of boradigermaallyl, which can also be regarded as a chloroborylene stabilzed by two germylene donors, with thiophene, furan, pyridazine and 2,2'-bipyridine are presented. Insertion the boron atom into heterocycles is observed resulting continue to react bis(germylene) molecule.

The planar, non-twisted distannene Sn2(TIPS)4 (1, TIPS = SiiPr3) reacts with CS2 to form a tetrathiaethylene derivative via the dimerization of two S-heterocyclic carbenes (SHCs). These intermediary-formed SHCs can be transferred palladium as ligands or captured B(C6F5)3 (BCF) and, furthermore, facilitate new pathway for formation stannaethene SHC═Sn(TIPS)2 by reaction 1 (PPh3)2Pd-CS2. In addition characterization complexes, theoretical calculations frontier orbitals were performed, which...

A one‐pot synthesis for previously unknown heavy homologues of group 9 metal carbynes [(Me3P)3CoºGeAr*] (1), [(Me3P)3RhºGeAr*] (2), [(Me3P)3IrºGeAr*] (3), [(Me3P)3IrºSnAr*] (5), and [(Et3P)3IrºPbAr*] (7) is presented [Ar* = C6H3‐2,6‐(Trip)2, Trip 2,4,6‐C6H2iPr3]. During these preparations the tetrylidynes [(Me3P)3RhºSnAr*] (4), [(Me3P)3RhºPbAr*] (6), were also prepared in a procedure. In hitherto metathetical exchange reaction transition plumbylidynes converted into respective stannylidynes...

A one‐pot synthesis for previously unknown heavy homologues of group 9 metal carbynes [(Me3P)3CoºGeAr*] (1), [(Me3P)3RhºGeAr*] (2), [(Me3P)3IrºGeAr*] (3), [(Me3P)3IrºSnAr*] (5), and [(Et3P)3IrºPbAr*] (7) is presented [Ar* = C6H3‐2,6‐(Trip)2, Trip 2,4,6‐C6H2iPr3]. During these preparations the tetrylidynes [(Me3P)3RhºSnAr*] (4), [(Me3P)3RhºPbAr*] (6), were also prepared in a procedure. In hitherto metathetical exchange reaction transition plumbylidynes converted into respective stannylidynes...

Dimers with very different RuRu bond lengths and RuClRu angles—deformation isomers—are present in equal parts crystals of the title compound. Solid-state NMR investigations show that isomer 1 a shorter distance (2.93 Å) is diamagnetic, longer (3.75 Å, b), on other hand, paramagnetic. The temperature dependence 1H signal solution understandable if one assumes two isomers rapidly interconvert.

The chemistry of the stanna-closo-dodecaborate cluster is summarized in this account. This dianionic group 14 heteroborate a versatile ligand coordination and can employ various modes. Our contributions to field are described with regard different transition-metal centers, which also coincide roughly chronological order contributions.

The reaction of MeNHC (MeNHC = 1,3,4,5-tetramethylimidazolylidene, where NHC N-heterocyclic carbene) adducts to organotin(II) hydrides Ar*SnH and Ar'SnH [Ar* 2,6-Trip2C6H3, Trip 2,4,6-triisopropylphenyl; Ar' 2,6-Mes2C6H3, Mes 2,4,6-trimethylphenyl)] with Lewis acids such as B(C6F5)3 or [CPh3]+ allows the abstraction hydride thus generation cationic, dicoordinate bis(σ-C)-substituted stannylenes [ArSn(NHC)]+. supposedly constitution this cationic stannylene was investigated by NMR...

Boradigermaallyl, valence-isoelectronic to an allyl cation, stabilized by Ge-bound C 6 H 3 -2,6-(Trip) 2 (Trip = 2,4,6-C i Pr ) groups shows triple insertion of ethylene into the Ge-B bonds ( or addition styrene at...

The tetrasubstituted polyanions of platinum, palladium, and gold [M(SnB(11)H(11))(4)](x-) (x=6, M=Pd, Pt; x=5, M=Au) have been prepared characterized by single-crystal X-ray diffraction, elemental analysis, IR, Raman, (11)B, (119)Sn heteronuclear NMR spectroscopy. In the case platinum derivative [Bu(3)MeN](6)[Pt(SnB(11)H(11))(4)] (2) Mössbauer spectroscopy has carried out. isolated salts are stable towards moisture air complexes 2 3 were treated with 1,3-bis(diphenylphosphino)propane (dppp)...

Aiming high: The coordination of the tin ligand stanna-closo-dodecaborate at Ni, Pd, and Pt results in formation compounds with high negative charges. These complexes contain metal centers numbers formal oxidation states. In case platinum derivative, a far upfield chemical shift 195Pt NMR spectrum (δ=−7724 ppm) was observed.