Reaction of [Cp*Fe(CO)2I] (Cp* = η5-C5Me5) with an excess amount of BH3·thf in toluene at 75 °C or with LiBH4 at -78 °C leads to the isolation of hydrogen-rich ferraborane arachno- [Cp *Fe(CO)B3H8] in good yield. In a similar fashion, reaction of [Cp*M(CO)3Cl] (M = Mo and W) with an excess amount of BH3·thf at 80 °C or at -78 °C with LiBH4 yielded metallaboranes [(Cp*M) 2B5H9] (M = Mo, W). Isolated yields of closo-[(Cp*M)2B5H9], (M = Mo and W), both from LiBH4 and BH3·thf, are good. All compounds were characterized in solution by IR, 1H, 11B, and 13C NMR spectroscopy and mass spectrometry and the structural types were unequivocally established by crystallographic analysis of arachno- [Cp*Fe(CO)B3H8]. (© Wiley-VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2009).

Sundargopal Ghosh

Department Of Chemistry

Goutam Pramanik

Tanmoy Kumar Saha

Venkatachalam Ramkumar

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

European Journal of Inorganic Chemistry

The thermolysis of arachno-1 [(Cp*Ru) 2 (B 3 H 8 )(CS 2 H)] in the presence of tellurium powder yielded a series of ruthenium trithia-borinane complexes: [(Cp*Ru) 2 (η 1 -S)(η 1 -CS){(CH 2 ) 2 S 3 BH}] 2, [(Cp*Ru) 2 (η 1 -S)(η 1 -CS){(CH 2 ) 2 S 3 B(SMe)}] 3, and [(Cp*Ru) 2 (η 1 -S)(η 1 -CS){(CH 2 ) 2 S 3 BH}] 4. Compounds 2-4 were considered as ruthenium trithia-borinane complexes, where the central six-membered ring {C 2 BS 3 } adopted a boat conformation. Compounds 2-4 were similar to our recently reported ruthenium diborinane complex [(Cp*Ru){(η 2 -SCHS)CH 2 S 2 (BH 2 ) 2 }]. Unlike diborinane, where the central six-membered ring {CB 2 S 3 } adopted a chair conformation, compounds 2-4 adopted a boat conformation. In an attempt to convert arachno-1 into a closo or nido cluster, we pyrolyzed it in toluene. Interestingly, the reaction led to the isolation of a capped butterfly cluster, [(Cp*Ru) 2 (B 3 H 5 )(CS 2 H 2 )] 5. All the compounds were characterized by 1 H, 11 B{ 1 H}, and 13 C{ 1 H} NMR spectroscopy and mass spectrometry. The molecular structures of complexes 2, 3, and 5 were also determined by single-crystal X-ray diffraction analysis. © 2019 by the authors.

Fulltext

Inorganics

Synthesis of trithia-borinane complexes stabilized in diruthenium core: [(Cp*Ru) 2 (η 1 -S)(η 1 -CS){(CH 2 ) 2 S 3 BR}] (R = H or SMe)

In an attempt to expand the library of M 2 B 5 bicapped trigonal-bipyramidal clusters with different transition metals, we explored the chemistry of [Cp*WCl4] with metal carbonyls that enabled us to isolate a series of mixed-metal tungstaboranes with an M 2 [B 4 M'] [M =W; M' = Cr(CO) 4 , Mo(CO) 4 , W(CO) 4 ] core. The reaction of in situ generated intermediate, obtained from the low temperature reaction of [Cp*WCl 4 ] with an excess of [LiBH 4 ·thf], followed by thermolysis with [M(CO) 5 ·thf] (M = Cr, Mo and W) led to the isolation of the tungstaboranes [(Cp*W) 2 B 4 H 8 M(CO) 4 ], 1-3 (1: M = Cr; 2: M = Mo; 3: M = W). In an attempt to replace one of the BH-vertices in M 2 B 5 with other group metal carbonyls, we performed the reaction with [Fe 2 (CO) 9 ] that led to the isolation of [(Cp*W) 2 B 4 H 8 Fe(CO) 3 ], 4, where Fe(CO) 3 replaces a [BH] core unit instead of the [BH] capped vertex. Further, the reaction of [Cp*MoCl 4 ] and [Cr(CO) 5 ·thf] yielded the mixed-metal molybdaborane cluster [(Cp*Mo) 2 B 4 H 8 Cr(CO) 4 ], 5, thereby completing the series with the missing chromium analogue. With 56 cluster valence electrons (cve), all the compounds obey the cluster electron counting rules. Compounds 1-5 are analogues to the parent [(Cp*M) 2 B 5 H 9 ] (M= Mo and W) that seem to have generated by the replacement of one [BH] vertex from [(Cp*W) 2 B 5 H 9 ] or [(Cp*Mo) 2 B 5 H 9 ] (in case of 5). All of the compounds have been characterized by various spectroscopic analyses and single crystal X-ray diffraction studies. © 2019 by the authors.

Synthesis, structures and chemistry of the metallaboranes of group 4-9 with M 2 B 5 core having a cross cluster M-M bond

In an effort to synthesize metallaheteroborane complexes of ruthenium, we carried out the reaction of ruthenium methanedithiolate complex, [(Cp∗Ru)2(B3H8)(CS2H)], (Cp∗ = η5-C5Me5) 1 with [BH3SPh]Li at elevated temperature that yielded a dinuclear bridged thiolate complex [Cp∗Ru(µ-SPh)2(µ-η1-S2)RuCp∗], 2. In a similar fashion, reaction of [Cp∗IrCl2]2 with [BH3TePh]Li yielded tellurolato-bridged diiridium half sandwich complex [Cp∗IrH(µ-TePh)2HIrCp∗], 5. All the compounds have been characterized by various spectroscopic techniques and the structures were unequivocally established by crystallographic analysis. Further, the density functional theory (DFT) calculations were performed to investigate the bonding and electronic properties of 2′ and 5′ (Cp analogues of 2 and 5). © 2018

Inorganica Chimica Acta

Chalcogenolato-bridged dinuclear half sandwich complexes of ruthenium and iridium

To build upon our earlier results of heterometallic metallaboranes employing metal carbonyls, we performed the reaction of nido-[(Cp*Rh)2B3H7] (1) (nido-1) with [M(CO)5·THF] (M = Mo or W) that yielded the trimetallic metallaborane clusters [(Cp*Rh)2M(CO)3(μ-CO)(μ3-BH)(B2H4)] (3: M = Mo; 4: M = W) having a capped borylene fragment and trimetallic triply bridging borylene complexes [(Cp*Rh)2(μ3-BH)(μ-CO)M(CO)5] (5: M = Mo; 6: M = W). The chemistry of trimetallic triply bridging borylene complexes (5 and 6) were explored with Lewis bases such as tert-butyl isocyanide and bisphosphine ligands. Photolysis of 5 and 6 with tert-butyl isocyanide yielded [(Cp*Rh)2(μ3-BH)(μ-CO)M(CO)4(CN-tBu)] (7: M = Mo; 8: M = W) and with phosphines, PPh2(CH2)nPPh2 (n = 1, 2) they resulted in the formation of [(Cp*Rh)2(μ3-BH)(μ-CO)M(CO)4((PPh2)2(CH2)n)] (9: n = 1, M = Mo; 10: n = 1, M = W; 11: n = 2, M = Mo; 12: n = 2, M = W). All the new compounds have been characterized in solution by mass spectrometry and NMR spectroscopic techniques. The structural aspects were unambiguously established by X-ray crystallographic analysis of 3–4 and 7–10. © 2018 Elsevier B.V.

Journal of Organometallic Chemistry

Synthesis and ligand substitution of tri-metallic triply bridging borylene complexes

The chemistry of ruthenium–borane complex, [Cp∗RuCO(μ-H)BH2L] (Cp∗ = η5-C5Me5; L = C7H4NS2), 1 with various alkynes has been explored. Photolysis of 1 with alkynyl-Grignard, [HC[tbnd]CMgBr] in toluene led to the isolation of vinyl hydroborate complex [Cp∗Ru(μ-H)BH{HC[dbnd]CH2}L], 2a as a sole product. Compound 2a can be viewed as a ruthenium–borate complex with an ethylene moiety. Further, the chemistry of 1 with various internal and terminal alkynes has been performed in photolytic conditions. Photolysis of 1 with [RC[tbnd]CR] (R = CO2Me) yielded vinyl hydroborate complex [Cp∗Ru(μ-H)BCl{RC[dbnd]CR}L], 2b. Terminal alkynes [HC[tbnd]CR] (R = Ph or CO2Me) under the same reaction conditions led to the isolation of metal vinyl complexes [Cp∗Ru(CO)(C2HR)(L)], 3a and 3b (3a: R = Ph; 3b: R = CO2Me). In addition, DFT calculations were carried out to analyze the bonding and electronic structures of these new compounds. © 2017 Elsevier Ltd

Polyhedron

Chemistry of ruthenium σ-borane complex, [Cp∗RuCO(μ-H)BH2L] (Cp∗ = η5-C5Me5; L = C7H4NS2) with terminal and internal alkynes: Structural characterization of vinyl hydroborate and vinyl complexes of ruthenium

Formation of ferraboranes from pentaborane(9) or BH3·thf and an electron-rich cyclopentadienyl iron phosphine hydride

Organometallics

Synthesis and Interconversion of Some Small Ruthenaboranes: Reaction of a Ruthenium Borohydride with Pentaborane(9) to Form Larger Ruthenaboranes

Angewandte Chemie International Edition

Synthesis and Characterization of [exo-BH2(Cp*M)2B9H14] (M=Ru, Re), and the Conversion of the Ruthenaborane into [(Cp*Ru)2B10H16] with an Open Cluster Framework Based on a Capped Truncated Tetrahedron

Synthesis and structure of [(η5-C5Me5)WCl2(μ-H)]2. A dinuclear tungsten hydride with a double bond formed from the reaction of BH3THF with (η5-C5Me5)WCl4

Journal	Data powered by TypesetEuropean Journal of Inorganic Chemistry
Publisher	Data powered by TypesetWiley-VCH Verlag
ISSN	14341948
Open Access	No