The reaction of (η5-C5H5)Ni(SIMes)Cl with n-propylmercaptane and NEt3 in CH2Cl2 affords the thiolate carbene nickel complex (η5-C5H5)Ni(SIMes)SnPr (I) (SIMes is 1,3-dimesitylimidazol-2-ylidene), which reacts with W(CO)5(THF) to form the heterometallic complex (η5-C5H5)Ni(SIMes)(μ2-SnPr)W(CO)5 (II). The reaction of complex I with (η5-С5H5)Mn(CO)2(THF) affords compound (η5-C5H5)Ni(SIMes)(μ2-SnPr)(η5-С5H5)Mn(CO)2 (III). The structures of compounds I, II, and III are determined by X-ray structure analysis (CIF file CCDC nos. 2024873 (I), 2024874 (II), and 2024875 (III)). According to the data of thermogravimetry and differential scanning calorimetry, the thermal decomposition of complexes II and III occurs stepwise in ranges of 101–500 and 119–550°С, and no ligand elimination is observed.

The reactions of Cd(NO3)2 ⋅ 4H2O with 2-amino-5-bromopyridine (Аbp) afford compounds [Cd(NO3)2(Аbp)(H2O)]n (I) and [Cd(NO3)2(Abp)2(H2O)2] (II). The structures of both complexes are determined by single-crystal X-ray structure analysis (CIF files CCDC nos. 1938624 (I) and 1959680 (II)). Compound I is a coordination 1D polymer in which two chelate-bonded $${\text{NO}}_{3}^{ - }$$ groups act as bridges. The coordination polyhedron of the octacoordinated central cadmium atom in compound I consists of seven oxygen atoms (one oxygen atom of water and six atoms of the $${\text{NO}}_{3}^{ - }$$ groups) and one nitrogen atom of Abp, being a triangular dodecahedron. Complex II is a mononuclear molecule in which the octahedral coordination polyhedron of Cd is formed by four oxygen atoms of two water molecules and two $${\text{NO}}_{3}^{ - }$$ groups and two oxygen atoms of two molecules of the Abp cycle. In both complexes, the amino group of Abp is not involved in coordination with the metal. Compound I is studied by 1H, 31C, and 15N NMR spectroscopy of a solution of the polymer complex in CD3CN, and the most substantial difference in the chemical shifts of the bound and free Abp ligands is observed in the 15N NMR spectra (37 ppm). According to the data of luminescence spectroscopy, compounds I and II exhibit an emission in a range of 430–690 nm.

Formal substitution of aryl group on to the ferrocenyl in [CpFe(CO)(mu-TeR)](2) (R = Ar, Fc) complex dramatically changes its Fe2Te2 core structure and chemical properties. Introduction of electron-rich and bulky ferrocenyl moiety instead of Ph in [CpFe(CO)TePh](2) provide flattening of Fe2Te2 core in [CpFe(CO)(mu-TeFc)](2) (1), further photochemical decarbonylation resulting unusual [(CpFe)(3)(mu-TeFc)(3)(mu-CO)(CO)] cluster (2). The electrochemical oxidation of 1 shows two reversible one-electron oxidation waves attributed to oxidation of Fe2Te2 core. Chemical oxidation of 1 is accompanied by isomerization of its core and results in dicationic salt cis-[CpFe(CO)(mu-TeFc)](2) (PF6)(2) (3). This study also provides an illustrative example of the increasing nuclearity in Fe-1 -> Fe-2 -> Fe-3 row, upon the stepwise electron-compensating decarbonylation of iron-carbonyl complexes and (apart from this) insight into the distribution of toluene molecules inclusion inside the channels of crystals of compound 2. (C) 2019 Elsevier Ltd. All rights reserved.

o-Ferrocenylcarbonylbenzoic acid (η5-C5H5)Fe(η5-C5H4C(O)C6H4COOH) (I) and o-cymantrenylcarbonylbenzoic acid (II) were obtained from ferrocene or (η5-C5H5)Mn(CO)3, respectively, by the Friedel–Crafts reaction with phthalic anhydride. Methyl o-ferrocenylcarbonylbenzoate (η5-C5H5)Fe(η5-C5H4C(O)C6H4COOMe (III) and methyl o-cymantrenylcarbonylbenzoate (CO)3Mn(η5-C5H4C(O)C6H4COOMe) (IV) were synthesized from I and II, respectively using dimethyl carbonate (DMC) in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) to promote the methylation reaction. 4-Ferrocenylphthalazin-1(2H)-one (V) and 4-cymantrenylphthalazin-1(2H)-one (VI) were obtained by the interaction of hydrazine hydrate with I and II, respectively, by the prolonged reflux or convenient solvothermal synthesis. Cyclic voltammetry measurements showed that compounds III and V undergo reversible one-electron oxidation, localized presumably at the ferrocene unit. For III the irreversible one-electron oxidation is apparently associated with the oxidation of the benzoate fragment. All new compounds were characterized by spectroscopic methods and the molecular structures of II and III were determined by X-ray diffraction analysis.

By the reaction of tetramer [Me3Pt(mu(3)-Cl)](4) with RhCl3 and [PPN] Cl (PPN - Ph3P - N - PPh3+) in a acetone-DCM mixture under the influence of ultrasound a heterometallic ionic complex [PPN][Me3Pt(mu-Cl)(3)Rh(mu-Cl) 3PtMe3] (I) have been prepared. Tetranuclear complex [PPN](2) [(Me3Pt)(2)Ru-2(m-O)(m-Cl)(6)Cl-4](2-)(II) have been obtained in a small yield starting from RuCl3 in similar conditions. Complex II has also been prepared purposefully in higher yield by the action of Me3Pt(Me2CO)(3)][PF6] on [PPN](4)[Ru2OCl10]. Both complexes were characterized by elemental analysis, H-1, C-13, and Pt-195 NMR spectroscopy, and their structures were determined by single crystal X-ray diffraction. (c) 2019 Elsevier B.V. All rights reserved.

Tungsten cycloheptatrienyl complexes (η 7 -C 7 H 7 )W(CO) 2 I ( I ), [(η 3 -C 7 H 7 )W(CO) 2 (CH 3 CN) 3 ]PF 6 ( II ), and [(η 7 -C 7 H 7 )W(CO) 2 (CH 3 CN)]PF 6 ( III ) (CIF files CCDC nos. 1875096 ( I ), 1875097 ( II ), 1875098 ( III )), characterized earlier only by spectroscopic methods, were prepared and studied by X-ray diffraction. The tris(acetonitrile) complex II can lose two acetonitrile ligands in both coordinating and non-coordinating solvents with the η 3 → η 7 change in the hapticity of the cycloheptatrienyl ring to be converted to III . The reverse ligand attachment process with the η 7 → η 3 change in the hapticity of the cycloheptatrienyl ring takes place upon the dissolution of monoacetonitrile complex III in acetonitrile. The electron-compensating η 3 ↔ η 7 change in the hapticity of the tropylium ligand is reversible.

The rhenium complexes TpReOCl(S t Bu) ( I ), TpReO(S t Bu) 2 ( II ), and TpReO(S n C 3 H 7 ) 2 ( III ) are synthesized using two methods by analogy to the known thiophenyl complexes. Complexes I – III having more electron-donating alkylthiolate ligands are characterized by IR and NMR spectroscopy. The structures of complexes I–III are determined by X-ray diffraction analysis (СIF files CCDC nos. 1892096 ( I ), 1892097 ( II ), and 1892098 ( III )). The temperature dependence of the spectra of the bis(thiolate) complexes allows one to determine the activation energy for the hindered rotation about the Re–thiolate ligand bond. The by-product of the reaction of TpReOCl 2 with NaS- tert -Bu, binuclear oxygen-bridged complex TpRe IV Cl(S- tert -Bu)O(S- tert -Bu) 2 Re IV Tp, is isolated and structurally characterized (СIF file CCDC no. 1892099).

Complex (η 5 -C 5 H 5 ) 2 Fe 2 (CO) 4 ( I ) reacts with 1,3-dimethylimidazolium-2-carboxylate Me 2 ImCO 2 to give asymmetric binuclear carbene iron complex (η 5 -C 5 H 5 ) 2 Fe 2 (CO) 3 (Me 2 Im) ( II ) (Me 2 Im = 1,3-dimethylimidazol-2-ylidene). The oxidation of compound II with elemental iodine proceeds via two mechanisms, symmetrical and asymmetrical, to form four products: (η 5 -C 5 H 5 Fe(CO) 2 (Me 2 Im)I ( III ), (η 5 -C 5 H 5 )Fe(CO) 2 I ( IV ), (η 5 -C 5 H 5 Fe(CO) 2 (Me 2 Im)I 3 ( V ), and ferrocene ( VI ). In each case, two pairs of reaction products have formed, two of which include NHC ligand: neutral iron(III) complex and ionic complex V. Optimal synthesis conditions to obtain preferably one of these complexes have been found. Geometry and transition state energy of supposed reaction mechanism have been calculated by quantum chemistry methods.

The reaction of ( p -cymene)Ru(Me 2 Im)Cl 2 with excess Me 2 ImCO 2 in acetonitrile in the presence of NH 4 PF 6 afforded the amino complex [( p -cymene)Ru(Me 2 Im)(NH 3 )Cl]PF 6 . The reaction of ( p ‑cymene)Ru(Me 2 Im)Cl 2 with excess anhydrous SnCl 2 gave the complex ( p -cy-mene)-Ru(Me 2 Im)Cl(SnCl 3 ), whereas treatment of dimeric iodide complex [( p -cymene)RuI 2 ] 2 with Me 2 ImCO 2 in acetonitrile gave the ionic compound [Me 2 ImH][( p -cymene)RuI 3 ]. CIF files: CCDC nos. 1841649 ( I ), 1841650 ( II ), 1841648 ( III ).

CpFe(CO)2TePh (I) can substitute one carbonyl group in Fe(CO)4I2 providing Fe(CO)3I2(μ-TePh)Fe(CO)2Cp (II) or play role of ligand to monomeric fragments [(p-Cymene)RuI2] and [Сp*RhI2] (p-Cymene = (η6-1-isopropyl-4-methylbenzene); Сp* = η5-pentamethylcyclopentadienyl) provides the complexes (p-Cymene)RuI2(μ-TePh)Fe(CO)2Cp (III) and Cp*RhCl2(μ-TePh)Fe(CO)2Cp (IV), respectively. The single-crystal X-ray diffraction of complexes II–IV (CIF files CCDC nos. 1038124 (II), 1038127 (III), 1038125 (IV)) revealed the shortening of М–Те bonds and the presence of intramolecular I…Te contacts.

Silver(I) nitrate complexes [AgNO 3 (L) 2 ], where L is quinoline or 2-, 4-, and 8-methylquinoline, are synthesized and studied by the multinuclear NMR ( 1 H, 13 C, 15 N) method in acetonitrile. The influence of steric and electronic factors of the organic ligand on the NMR spectral parameters is revealed. The fast chemical exchange of the free and coordinated ligands is observed at room temperature. The 15 N NMR spectra are most informative. The formation of a complex with 8-methylquinoline is impeded because of steric hindrances.

The complexes [AgL 2 (NO 3 )] ( I ) and [AgL 2 (CH 3 SO 3 )] · H 2 O ( II ) (L is 2-methylquinoline, C 10 H 9 N) have been synthesized and structurally characterized by single-crystal X-ray diffraction. Crystals of I are monoclinic, space group P 2 1 / n , a = 9.296(1) Å, b = 13.495(1) Å, c = 14.931(1) Å, β = 95.06(1)°, V = 1865.8(3) Å 3 , ρ calc = 1.624 g/cm 3 , Z = 4. Crystals of II are monoclinic, space group P 2 1 / n , a = 13.147(1) Å, b = 11.767(1) Å, c = 13.814(1) Å, β = 96.06(1)°, V = 2124.3(3) Å 3 , ρ calc = 1.599 g/cm 3 , Z = 4. Compounds I and II are composed of discrete complexes of similar structure but with different orientation of the methyl groups of ligand L ( trans and cis arrangement, respectively). Both anions, NO 3 - and CH 3 SO 3 - function as a chelating weakly bound ligand for the Ag + ion. The presence of water molecules in II is favorable for the formation of dimeric supramolecular moieties between the centrosymmetrically arranged Ag + complexes with 2-methylquinoline. The luminescence spectra of solid complexes I and II showed a bathochromic shift as compared to the spectrum of L in acetonitrile. Complexes I and II have been characterized by 1 H and 13 C{H} NMR spectra in CD 3 CN.