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Inorg Chem ; 59(3): 1917-1927, 2020 Feb 03.
Artigo em Inglês | MEDLINE | ID: mdl-31934757


Irradiation of [Re2(CO)10] in the presence of BH3·thf resulted in the formation of several rhenium diborane(6) species, for example, [{(OC)4Re}{Re(CO)3}2(µ3-η2:η2:η2-B2H6)(µ-H)], 1; [{(OC)4Re}2{Re(CO)3}(µ3-η2:η2:η1-B2H6)(µ-H)], 2; and [{(OC)4Re}2(µ-η2:η2-B2H6)], 3, comprising diverse coordination modes of the [B2H6]2- ligand. Compound 1 contains a tris(bidentate) [B2H6]2- unit, whereas 2 consists of an unsymmetrically bound [µ3-η2:η2:η1-B2H6]2- ligand. In contrast, the irradiation of [Mn2(CO)10] with BH3·thf yielded only the Mn analogue of 1, [{(OC)4Mn}{Mn(CO)3}2(µ3-η2:η2:η2-B2H6)(µ-H)], 1'. In an attempt to generate the bimetallic Mn-diborane(6), we have carried out the reaction of 1' with PCy3 under photolytic conditions. The reaction led to the formation of two single base stabilized unsymmetrical diborane(5) species, [{Mn(CO)3}{Mn(CO)2PCy3}(µ-η2:η2-B2H5·PCy3)(µ-H)], 4, and [{Mn(CO)2PCy3}(η3-B2H5·PCy3)], 5. As [B2H6]2- and [B2H5·PCy3]- are isoelectronic, the bondings in 4 and 5 are analogous to that of diborane(6) species 1-3. All the new species have been characterized spectroscopically, and their structures were further confirmed by single-crystal X-ray diffraction studies. DFT-type quantum chemical calculations were carried out that provided insight into the bonding interaction of [B2H6]2- and [B2H5·PCy3]- with the M(CO)n fragments.

Dalton Trans ; 48(22): 7953, 2019 06 14.
Artigo em Inglês | MEDLINE | ID: mdl-31089644


Correction for 'Mercapto-benzothiazolyl based ruthenium(ii) borate complexes: synthesis and reactivity towards various phosphines' by Mohammad Zafar, et al., Dalton Trans., 2019, DOI: 10.1039/c9dt00498j.

Dalton Trans ; 48(21): 7413-7424, 2019 06 07.
Artigo em Inglês | MEDLINE | ID: mdl-30994656


The synthesis and reactivity of ruthenium complexes containing an anionic boron based ligand, supported by mercapto-benzothiazolyl heterocycles are presented. Specifically, the reaction of [(η6-p-cymene)Ru{P(OMe)2OR}Cl2], (1a: R = Me; 1b: R = H) with [H2B(mbz)2]- (mbz = 2-mercaptobenzothiazolyl) at room temperature afforded a series of borate complexes, namely [(L)Ru{κ3-H,S,S'-H2B(L)2}P(O)(OMe)(HL)], 2, [Ru{κ3-H,S,S'-H2B(L)2}2], 3 and [(κ2-N,S-L)P(OMe)3Ru{κ3-H,S,S'-H2B(L)2}], 4a; (L = C7H4NS2). The pivotal feature of 2 is the coordination of the Ru centre with a phosphorus atom of secondary phosphine oxide and mercapto-benzothiazolyl ligands. On the other hand, 3 features dual RuH-B interactions between Ru and B-H bonds of [H2B(mbz)2]-. Interestingly, along with 3, compound [(κ2-N,S-L)P(OPh)3Ru{κ3-H,S,S'-H2B(L)2}], 4b (L = C7H4NS2), was isolated upon treatment of the same borate with [(η6-p-cymene)RuCl2P(OPh)3], 1c, which is stabilized by δ-B-H interactions and one phosphite ligand. Furthermore, compound 3 promptly reacts with P(OR)3 to generate [(OR)3PRu-{κ2-S,S'-H2B(L)2}{κ3-H,S,S'-H2B(L)2}], (5a: R = Me, 5b: R = Ph; L = C7H4NS2) by breaking one of the RuH-B interactions. Upon heating, compound 5a converts into [(OMe)2OPRu{κ2-S,S'-HB(L)2}{κ3-H,S,S'-H2B(L)2}], 6a (L = C7H4NS2) by release of methane gas. Compound 6a is a unique example wherein the boron atom of the borate ligand is bound to an oxygen atom of the phosphite unit. In contrast, the thermolysis of 3 with PR2R' yielded [Ru{κ3-H,S,S'-H2B(L2)}(PR2R')2(L)], (7a: R = Me, R' = Ph; 7b: R = Ph; R' = Me; L = C7H4NS2), respectively, revealing the incorporation of two triphosphine ligands in the coordination sphere of ruthenium. Density functional theory (DFT) calculations were undertaken to provide an insight into the electronic structures of the complexes.