Deprotonation of SiMe2(HNPbt)2 proligand (1) by Li(NTms2) (Tms = SiMe3) base results in the formation of SiMe2(LiNPbt)2 (Pbt = 2-(1,3-benzothiazol-2-yl)phenyl) in solution, which further reacts with GdCl3 yielding [Li(THF)4][Gd(SiMe2(NPbt)2)2] complex (2). In an attempt to obtain 2 with the use of n-butyllithium as a base, an unexpected product with an intricate structure - [GdMe2Si(NPbt)(o-NC6H4-C(Bu)2(o-NHC6H4S))(μ-NHPbt)Li(THF)] complex (3) is isolated and structurally characterized. The thiazole ring of one of the substituents of the silandiamide ligand is open in it, while two butyl groups are attached to the thiazole C2 carbon atom. In the reaction of 1 with an excess of butyllithium and YCl3, a product with the ligand also containing the C(Bu)2 moiety is formed, which is shown by 1H NMR. Apart from it, double complex salt [Li(THF)4][Y(SiMe2(NPbt)2)2] (4) crystallized as a solvate with Et2O is isolated from the reaction mixture. In an attempt to obtain a monosubstituted [Y(SiMe2(NPbt))Cl] complex, compound 4·2THF forms along with several crystals of [Y(SiMe2(NPbt)2)2(μ-OBu)2] complex (5) the structure of which is characterized by single crystal X-ray diffraction. The photophysical properties of compound 2 are studied in the THF solution and in the crystalline state.

Депротонирование пролиганда SiMe2(HNPbt)2 (1) основанием Li(NTms2) (Tms = SiMe3) приводит к образованию в растворе SiMe2(LiNPbt)2 (Pbt = 2-(1,3-бензотиазол-2-ил)фенил), который далее реагирует с GdCl3 с образованием комплекса [Li(thf)4][Gd(SiMe2(NPbt)2)2] (2). При попытке получения 2 c использованием н-бутиллития в качестве основания был выделен и структурно охарактеризован неожиданный продукт сложного строения — комплекс [Gd{Me2Si(NPbt)(o-NC6H4-C(Bu)2(o-NHC6H4S))}(μ-NHPbt)Li(thf)] (3), в котором тиазольный цикл одного из заместителей силандиамидного лиганда оказался раскрыт, а две бутильные группы присоединены к атому углерода С2 тиазола. В реакции 1 с избытком бутиллития и YCl3 образуется продукт с лигандом, также включающим фрагмент C(Bu)2, что было показано с помощью ЯМР 1H. Помимо него, из реакционной смеси была выделена двойная комплексная соль [Li(thf)4][Y(SiMe2(NPbt)2)2] (4), кристаллизующаяся в виде сольвата с Et2O. При попытке получения монозамещённого комплекса «[Y(SiMe2(NPbt))Cl]» образовалось соединение 4∙2thf, а также было выделено несколько кристаллов комплекса [{Y(SiMe2(NPbt)2)}2(µ-OBu)2] (5), охарактеризованного с помощью РСА. Для соединения 2 были исследованы фотофизические свойства в растворе в ТГФ и в кристаллическом виде.

По реакции Pbt-NHPPh2 и MesN3 (Pbt = 2-(бензотиазол-2-ил)фенил; Mes = мезитил) был синтезирован несимметричный аминоиминофосфоран Ph2P(NHPbt)(=NMes) (HL), который в дальнейшем был использован для синтеза комплекса [Y(L)Cl2(Thf)] (1) (Thf = тетрагидрофуран, ТГФ). Соединения выделены в виде кристаллических фаз HL, HLꞏ0.5PhMe, 1 и 1ꞏPhMe и охарактеризованы методами РСА, ЯМР- и ИК-спектроскопии. В HL присутствует водородная связь между атомом водорода NH группы, связанной с Pbt, и атомом азота гетероцикла. В комплексе 1 все три атома азота лиганда координированы к катиону иттрия, с образованием плоской структуры хелатных циклов. Как в HL, так и в комплексе 1 наблюдается π-стэкинг между ароматическими фрагментами молекул.

Binuclear complexes [Fe2(µ-S2ER2)(CO)6] (ER2 = SiMe2 (Iа), SiEt2 (Ib), SnEt2 (Ic)), promising precursors of heterometallic clusters, were synthesized. Reactions of these complexes with transition metal halide complexes, [Cp"RhCl2]2 (Cp" = η5-C5H3tBu2), [(Dppe)NiCl2] (Dppe = Ph2PCH2CH2PPh2), [(Ph3P)AuCl], and [Mn(CO)5Cl], were studied. The reactions gave heterometallic clusters [Fe2Rh(µ3-S)2(CO)6Cp"] (II), [Fe2Ni(µ3-S)2(CO)6(Dppe)] (III), [Fe2(CO)6(µ-SSnClEt2)(µ-SAu(PPh3))] (IV), [Fe2(CO)6(µ4,η2-S2SnEt2){Mn(CO)4Cl}2] (V), and [Fe2Mn(CO)9Mn(CO)5(µ3-S)(µ4-S)] (VI). Cluster V was found to be converted to VI upon photochemical activation. The structures of compounds I–VI were determined by X-ray diffraction (CIF file CCDC nos. 751214 (Ic), 751215 (III·0.5C7H8), 2062206 (V), 2062207 (Ib), 2062208 (Ia), 2062209 (IV·0.5CH3C5H9).

The electrochemical properties of sixteen tri- and tetranuclear chalcogenide-bridged heterometallic clusters in comparison with the tetrahedral clusters Cp′4M4S4 (M = Cr, V; Cp′ = CH3C5H4) simulating ferredoxins were studied. For complexes with μ4-coordination of the chalcogen, only reduction processes involving the metal-heterometal bonds are reversible. For complexes with μ3-coordination of the chalcogen, the oxidation processes are reversible except for triiron-chalcogen-pnicogenide clusters having an easily and reversibly oxidizable E-Fe(CO)2C5H4Bu-t bond (E = Sb, Bi) at the pnicogen atom. The electron-compensating role of the lone pair at the bridging chalcogen atom in the stabilization of the oxidation products of the clusters is discussed.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Reactions of the arsinechalcogenide complexes [Fe 3 (μ 3 -X)(μ 3 -AsCH 3 )(CO) 9 ] (X = Se ( Ia ) or Te ( Ib )) with (PPh 3 ) 2 Pt(PhC≡CPh) (transmetalation reaction) and Cp 2 Cr 2 (SCME 3 ) 2 S (Cp = π-C 5 H 5 ) (photochemical reaction) gave the heterometallic (heterochalcogen)(methylarsine) clusters [(PPh 3 ) 2 Pt(μ 3 -X)(μ 3 -AsCH 3 )Fe 2 (CO) 6 ] ( II and III , respectively), as well as Fe 3 (μ 3 -X)(μ 3 -AsCH 3 )(CO) 8 (C 5 H 5 ) 2 Cr 2 (μ 3 -S)(μ 2 -S t Bu) 2 ( IV and V , respectively). The structures of complexes II, IV , and V were determined by X-ray diffraction analysis. Thermolysis of all the complexes yielded no metal carbides or oxides.

Cothermolysis of the clusters [Fe 3 (μ 3 -Q)(μ 3 -AsCH 3 )(CO) 9 ] (Q = Se and Te) and the complexes [Cp*M(CO) 2 ] (M = Rh and Ir) was accompanied by isolobal replacement of the fragment {Fe(CO) 3 } by {Cp*M}; the final reaction products were [Fe 2 M(μ 3 -Q)(μ 3 -AsCH 3 )(CO) 6 Cp*]. For M = Ir, these reactions involved addition of an iridium fragment to the starting cluster to give the intermediate adducts [Fe 3 Ir(μ 4 -Q)(μ 4 -AsCH 3 )(CO) 8 Cp*]. In the case of [Cp*Rh(CO) 2 ], the intermediate tetranuclear rhodium adducts were also isolated. Sets of these adducts differed for the selenide ([Fe 3 Rh(μ 4 -Se)(μ 4 -AsMe)(CO) 8 Cp*] and [Fe 2 Rh 2 (μ 3 -Se)(μ 4 -AsMe)(CO) 6 Cp 2 * ]) and telluride clusters ([Fe 3 Rh(μ 4 -Te)(μ 3 -AsMe)(μ-CO)(CO) 9 Cp*] and [Fe 3 Rh 2 (μ 3 -Te)(μ 4 -AsMe)(μ 3 -CO)(μ-CO)(CO) 8 Cp 2 * ]). The structures of all 10 novel heterometallic clusters were determined by single-crystal X-ray diffraction analysis.