Attractive metallophilic (aurophilic, argentophilic, cuprophilic, etc.) interactions play an important role in arrangement and stabilization of oligonuclear metal ion complexes. We report a combined experimental theoretical assessment aurophilic closed-shell gold(I) dimers. The binding energies were obtained for charged [(LH)AuCl]+...[(L′)AuCl] dimers (L is either phosphine or N-heterocyclic carbene ligand) the gas phase. These served benchmarking correlated quantum chemical calculations...

N,C,N-Chelated pnictinidenes ArE [where E = As (1), Sb (2) or Bi (3); Ar C6H3-2,6-(CH[double bond, length as m-dash]Nt-Bu)2] were used ligands for the coordination of transition metal carbonyls. Thus, reaction 1-3 with [M(CO)5THF] (where M Cr, W) [Mo(CO)5(Me3N)] gave complexes [(ArE)M(CO)5] and Cr (1a), Mo (1b), W (1c); (2a), (2b), (2c); (3a), (3b), (3c)]. Analogously, treatment [Fe2(CO)9] resulted in formation [(ArE)Fe(CO)4] (1d), (2d) (3d)]. All compounds characterized by 1H 13C NMR...

Abstract The reduction of N,C,N‐chelated antimony(III) chlorides [C 6 H 3 ‐2,6‐(CH=NR) 2 ]SbCl (R=Ph ( 1 ), t Bu Dip ); Dip=2,6‐ i Pr C ) with an appropriate amount KC 8 or Li[AlH 4 ] resulted in the formation rare examples monomeric stibinidenes ]Sb 5 )). Similarly, compounds by two equivalents K[B( s Bu) H] led to and . In contrast, analogous reaction compound unprecedented stibinidene ‐2‐(CH=NR)‐6‐(CH NHR)]Sb 7 (R=Dip), which hydrogen atoms that come from are incorporated into ligand...

Homobimetallic metallophilic interactions between copper, silver, and gold-based [(NHC)MX]-type complexes (NHC=N-heterocyclic carbene, i.e, 1,3,4-trimethyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene; X=F, Cl, Br, I) were investigated by means of ab initio interaction energies, Ziegler-Rauk-type energy-decomposition analysis, the natural orbital for chemical valence (NOCV) framework, noncovalent (NCI) index. It was found that dimers these predominantly adopt a head-to-tail arrangement with...

Generating monovalent pnictogens within NCN pincers has resulted in the isolation of three distinct types 1,2-azaheteroles, highly aromatic nitrogen analogues like pyrazole-based 5, yet fluxional P- and As-derived bell-clappers 1 2, hypervalent Sb Bi derivatives 3 4, which are supported by 3-center, 4-electron N–E–N bonds. Careful analysis solid-state structures 1–5/[5-Me][OTf] combination with NICS calculations (at GIAO/M06/cc-pVTZ(-PP) level) other computational methods (NBO) suggest that...

Treatment of N,C,N-chelated organopnictogen(I) compounds ArE (1-3) (Ar=2,6-(RN=CH)2 C6 H3 , E/R=As/Dmp (1), Sb/tBu (2), and Bi/tBu (3), where Dmp=2,6-Me2 ) with various electron-deficient alkynes RC≡CR' (R/R'=CO2 Me (DMAD), R/R'=H/CO2 Me, or R/R'=NC5 F4 affords different types heterocyclic compounds. In these reactions, 1-3 act as hidden dienes participate in hetero-Diels-Alder (DA) a feature that has been only rarely reported for heavier pnictogen this way, reactions 1 furnished the set...

Six palladium(II) complexes bearing three different triazole-based N-heterocyclic carbene (NHC) ligands, [1-tert-butyl-4-{2-[(N,N-dimethylamino)methyl]phenyl}-3-phenyl-1H-1,2,4-triazol-4-ium-5-ide, 1-tert-butyl-4-(2-methoxyphenyl)-3-phenyl-1H-1,2,4-triazol-4-ium-5-ide, and 1-tert-butyl-4-(4-methylphenyl)-3-phenyl-1H-1,2,4-triazol-4-ium-5-ide], were synthesized fully characterized. NMR spectroscopy X-ray diffraction analysis revealed that the amino-group-substituted NHC ligand is coordinated...

The complexation chemistry of the stannylene Sn{N[Si(CH3)3]2}2, first reported by Lappert in 1970s, was investigated 119Sn NMR chemical shift measurements. To this end, experimental data and theoretical density functional theory (DFT) calculations were combined to get an insight into interaction between various solvent molecules with σ- and/or π-coordinating power. Small variations measured shifts revealed a donor–acceptor molecules. In comparison noncoordinating cyclohexane taken as...

Reaction of 2-[(dimethylamino)methyl]aniline with butyllithium, followed by conversion trimethylsilyl, triphenylsilyl, triphenylgermyl, trimethylstannyl, or tri-n-butylstannyl chloride, gives the corresponding substituted aniline. These compounds were further deprotonated butyllithium and reacted germanium, tin, lead dichlorides, respectively, in both stoichiometric ratios 2:1 1:1, providing target homo- ([2-(Me(2)NCH(2))C(6)H(4)(YR(3))N](2)M) heteroleptic...

Non-covalent interactions were revealed in the complete series of coinage metal complexes type (NHC)MX (M = Cu, Ag, Au; X Cl, Br, I) bearing 1,2,4-triazole based NHCs.

Novel pnictogen(<sc>i</sc>) → Au(<sc>i</sc>) complexes were isolated including a unique example of the bismuthinidene complex containing first Bi(<sc>i</sc>) bond.

Two gold(I) complexes of the (NHC)AuX type bearing a triazole‐based N ‐heterocyclic carbene (NHC) ligand (1‐ tert ‐butyl‐4‐(4‐methylphenyl)‐3‐phenyl‐1 H ‐1,2,4‐triazol‐4‐ium‐5‐ylidene) and various halide ligands (X = Br, I) were synthesized characterized in solution using NMR spectroscopy as well solid state X‐ray diffraction techniques. The cytotoxic properties both compounds precursor, (NHC)AuCl, screened against panel human tumour cell lines including liver cancer (HepG2), cervical (HeLa...

Abstract The drive to develop maximal atom‐efficient catalysts coupled the continuous striving for more sustainable reactions has led an ever‐increasing interest in single‐atom catalysis. Based on a periodic conceptual density functional theory (cDFT) approach, fundamental insights into reactivity and adsorption of single late transition metal atoms supported fully hydroxylated amorphous silica surface have been acquired. In particular, this investigation revealed that influence van der...

Abstract Our attempts to synthesise N→M intramolecularly coordinated diorganometallic hydrides L 2 MH [M=Si ( 4 ), Ge 5 Sn 6 )] containing the CH=N imine group (in which is C,N‐chelating ligand {2‐[(2,6‐ i Pr C H 3 )N=CH]C } − ) yielded 1,1′‐bis(2,6‐diisopropylphenyl)‐2,2′‐spriobi[benzo[ c ][1,2]azasilole] 7 ][1,2]azagermole] 8 and , N ‐chelated homoleptic stannylene 10 respectively. Compounds are an outcome of a spontaneous double hydrometallation two moieties induced by intramolecular...

The bonding in heavier Group 14 zero-valent complexes of a general formula L2 E (E=Si-Pb; L=phosphine, N-heterocyclic and acyclic carbene, cyclic tetrylene carbon monoxide) is probed by combining valence bond (VB) theory maximum probability domain (MPD) approaches. All studied are initially evaluated on the basis structural parameters shape frontier orbitals revealing bent motif presence two lone pairs at central atom. For VB calculations three resonance structures suggested, representing...

Abstract The 2,1‐benzazaarsole ( 1 ) showed a diene‐like reactivity towards selected alkynes RC≡CR (R=CO 2 Me, C 5 F 4 N) thus forming 1‐arsa‐1,4‐dihydro‐iminonaphthalenes and 3 as hardly isolable intermediates, that underwent facile CH→NH proton migration leading to before elusive substituted 1‐arsanaphthalenes b could be completely structurally characterized.

A set of neutral and ionic ruthenium arene trichlorostannyl complexes are reported herein. The tin(II) compounds L 1 SnCl { ; = [2‐(CH 2 NEt )‐4,6‐( t Bu) C 6 H ] – } [L SnCl][SnCl 3 2,6‐[(CH )C=N(C ‐2,6‐ i Pr ) ]C 5 N} showed a rather different reactivity towards the complex [(η ‐cymene)RuCl] (η‐Cl) . As consequence, [Ru(η ‐cymene)(L SnCl)Cl ( 4 compound SnCl][Ru(η ‐cymene)(SnCl Cl] 8 were isolated. insertion reaction with provided trimetallic SnCl)(SnCl )Cl] ). Analogous PPh )Cl )(SnCl 7...

A series of novel non-symmetric neutral N,N',O-chelating ligands derived from the α-iminopyridine 2-(C(R1)N(C6H3-2,6-iPr2))-6-(R2R3PO)C5H3N (L1: R1 = H, R2 R3 Ph; L2: Me, L3: H; Ph, EtO; L4: L5: iPrO; L6: iPrO) were synthesized. Ligands L1-6 reacted with SnCl2 and Sn(OTf)2 aim studying influence different R2R3PO functional groups on Lewis base mediated ionization Sn(OTf)2. While all provided corresponding ionic tin(II) complexes [L1-6 → SnCl]+[SnCl3]- (1-6), only L1, L4 L6 able to...

Novel organotin(<sc>iv</sc>) azides were employed as building blocks to prepare various tetrazolides or triazolides.

α-Iminopyridine ligands L1 (2-(CHN(C6H2-2,4,6-Ph3))C5H4N), L2 (2-(CHN(C6H2-2,4,6-tBu3))C5H4N) and L3 (1,2-(C5H4N-2-CHN)2CH2CH2) differing by the steric demand of substituent on imine CHN group number donating nitrogen atoms were utilized to initiate a Lewis base mediated ionization SnCl2 in an effort prepare ionic tin(II) species [L1-3 → SnCl][SnCl3]. The reaction with led formation neutral adducts [L1 SnCl2] (2) [L2 (3). preparation desired compounds was achieved subsequent reactions 2...

The rapidly growing interest for new heterogeneous catalytic systems providing high atomic efficiency along with stability and reactivity triggered an impressive progress in the field of single-atom catalysis. Nevertheless, unravelling factors governing interaction strength between support adsorbed metal atoms remains a major challenge. Based on periodic density functional theory (DFT) calculations, this paper provides insight into adsorption single late transition metals defect-free anatase...