The complexes [Ag{κ 3 -S,S′,H-H 2 B(mbz) 2 }(PR 3 )] x , (1: x = 2, R = Ph; 2: x = 1, R = Cy) (mbz = 2-mercaptobenzothiazolyl) and amidine based dihydro(2-mercaptobenzo-thiazolyl) borates, [HN=C(Ph)–NH(R)–H 2 B(mbz)] (3: R = 2,6-diisopropylphenyl and 4: R = Ph) were synthesized and characterized by various spectroscopic methods and single-crystal X-ray crystallography. Complex [Ag{κ 3 -S,S′,H-H 2 B(mbz) 2 }(PPh 3 )] 2 (1) has a dimeric structure in its crystalline state, in which central silver(I) atoms adopt a distorted trigonal bipyramid arrangement. In contrast, complex [Ag{κ 3 -S,S′,H-H 2 B(mbz) 2 }(PCy 3 )] (2) has a monomeric structure in its crystalline state, in which the central silver(I) atoms adopt a distorted trigonal planar arrangement. Infrared spectroscopy was utilized as a tool for investigating the presence of M···H–B interactions. In addition, density functional theory (DFT) calculations were used to analyse the B–H···[M] bonding interaction in the metal borate complexes. © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Sundargopal Ghosh

Department Of Chemistry

Suman Gomosta

Rongala Ramalakshmi

C. Arivazhagan

Anagha Haridas

Beesam Raghavendra

Kuppaiyandi Maheswari

IIT Madras is a public technical and research university located in Chennai, Tamil Nadu. Founded in 1959, it is recognised as an Institute of National Importance.

IIT Madras has been ranked as the top engineering institute in India for four years in a row by the National Institutional Ranking Framework of the MHRD

It currently offers undergraduate, postgraduate and research degrees across 16 disciplines in Engineering, Sciences, Humanities and Management. About 596 faculty belonging to science and engineering departments and centres of the Institute are engaged in teaching, research and industrial consultancy.

IIT Madras

Zeitschrift fur Anorganische und Allgemeine Chemie

Synthesis, Structural Characterization, and Theoretical Studies of Silver(I) Complexes of Dihydrobis(2-mercapto-benzothiazolyl) Borate

A series of new bis(σ)borate and agostic complexes of group 7 metals have been synthesized and structurally characterized from various borate ligands, such as trihydrobis(benzothiazol-2-yl)amideborate (Na[(H3B)bbza]), trihydro(2-aminobenzothiazolyl)borate (Na[(H3B)abz]), and dihydrobis(2-mercaptopyridyl)borate (Na[(H2B)mp2]) (bbza=bis(benzothiazol-2-yl)amine, abz=2-aminobenzothiazolyl, and mp=2-mercaptopyridyl). Photolysis of [Mn2(CO)10] with Na[(H3B)bbza] formed bis(σ)borate complex [Mn(CO)3(μ-H)2BHNCSC6H4(NR)] (1; R=NCSC6H4). Octahedral complex [Re(CO)2(N3C2S2C12H8)2] (2) was generated under similar reaction conditions with [Re2(CO)10]. Similarly, when [Mn2(CO)10] was treated with Na[(H3B)abz], bis(σ)borate complex [Mn(CO)3(μ-H)2BH(HN2CSC6H4)] (3) and the agostic complex [Mn(CO)3(μ-H)BH(HN2CSC6H4)2] (4) were formed. To probe the potential formation of agostic complexes of the heavier group 7 metals, we carried out the photolysis of [M2(CO)10] with Na[(H2B)mp2] and found that [M(CO)3(μ-H)BH(C5H4NS)2] (5: M=Re; 6: M=Mn) was formed in moderate yield. Complexes 1 and 3 feature a (κ3-H,H,N) coordination mode, whereas 4, 5, and 6 display both (κ3-H,N,N) and (κ3-H,S,S) modes of the corresponding ligands. To investigate the lability of the CO ligands of 1 and 3, we treated the complexes with phosphine ligands that generated novel bis(σ)borate complexes [Mn(μ-H)2(BHNCSC6H4)(NR)(CO)2PL2L’] (R=NCSC6H4; 7 a: L=L’=Ph; 7 b: L=Ph, L’=Me) and [Mn(μ-H)2BHN(NCSC6H4)R(CO)2PL2L’] (R=NCSC6H4; 8 a: L=L’=Ph; 8 b: L=Ph, L’=Me). Complexes 7 and 8 are structural isomers with different coordination modes of the bbza ligand. In addition, DFT calculations were performed to shed some light on the bonding and electronic structures of these complexes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Chemistry - A European Journal

Design, Synthesis, and Chemistry of Bis(σ)borate and Agostic Complexes of Group 7 Metals

A series of novel Cp*-based (Cp*=η5-C 5Me5) agostic, bis(σ-borate), and boratrane complexes have been synthesized from diruthenium and dirhodium analogues of pentaborane(9). The synthesis and structural characterization of the first neutral ruthenadiborane(6) analogue are also reported. This new route offers a very efficient method for the isolation of bis(σ-borate) and agostic complexes from diruthenapentaborane(9). © 2014 WILEY-VCH Verlag GmbH &amp; Co. KGaA, Weinheim.

Angewandte Chemie - International Edition

Reactivity of diruthenium and dirhodium analogues of pentaborane(9): Agostic versus boratrane complexes

The photolysis of [M2(CO)10] (M=Re or Mn) with BH3·thf at room temperature yields arachno-1 and 2, [(CO) 8M2B2H6] (1: M=Re, 2: M=Mn). Both the compounds show a butterfly structure with seven skeletal electron pairs and 42 valence electrons. This result presents a new method for general access to low-boron-content metal-boron compounds without the cyclopentadienyl ligand at the metal centers. This new synthetic route is superior to the existing procedures because it avoids the use of [LiBH4] and metal polychlorides, for which the synthesis is very tedious. Compound 1 catalyzes the cyclotrimerization of a series of internal and terminal alkynes to yield mixtures of 1,3,5- and 1,2,4-substituted benzenes. The reactivity of 1 with alkynes demonstrates for the first time that the introduction of the [B 2H6] moiety into the [Re2(CO)10] framework significantly enhances the catalytic activity. Note that [Re 2(CO)10] catalyzes the same set of alkynes under harsh conditions over a prolonged period of time. Quantum-chemical calculations using DFT methods are applied to afford further insight into the electronic structure, stability, and bonding of 1 and 2. All the compounds are characterized by IR and 1H, 11B, and 13C NMR spectroscopy, and the geometry of 1 is established unambiguously through crystallographic analysis. Arachno compounds: Room-temperature UV photolysis of [Re2(CO) 10] with BH3·thf yielded arachno-[(CO) 8Re2B2H6], which catalyzed the cyclotrimerization of various internal and terminal alkynes to yield mixtures of 1,3,5- and 1,2,4-substituted benzenes (see figure). Copyright © 2014 WILEY-VCH Verlag GmbH &amp; Co. KGaA, Weinheim.

Journal	Data powered by TypesetZeitschrift fur Anorganische und Allgemeine Chemie
Publisher	Data powered by TypesetWiley-VCH Verlag
ISSN	00442313
Open Access	No