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Although atomically precise polyhydrido copper nanoclusters are of prime interest for a variety of applications, they have so far remained scarce. Herein, this work describes the synthesis of a dithiophosphate‐protected copper(I) hydride‐rich nanocluster (NC), [Cu30H18{S2P(OnPr)2}12] (1H), fully characterized by various spectroscopic methods and single‐crystal X‐ray diffraction. The X‐ray structure of 1H reveals an unprecedented central Cu12 hollow icosahedron. Six faces of this icosahedron are capped by Cu3 triangles, the whole Cu30 core being wrapped by twelve dithiophosphate ligands and the whole cluster has ideal S6 symmetry. The locations of the 18 hydrides in 1H were ascertained by a single‐crystal neutron diffraction study. They are composed of three types: capping μ3‐H, interstitial μ4‐H (seesaw) and μ5‐H ligands (square pyramidal), in good agreement with the DFT simulations. The numbers of hydrides and ligand resonances in the 1H NMR spectrum of 1H are in line with their coordination environment in the solid state, retaining the S6 symmetry in solution. Furthermore, two new Se‐protected polyhydrido copper nanoclusters, [Cu30H18{Se2P(OR)2}12] (2H: R=iPr 3H: R=iBu) were synthesized from their sulfur relative 1H via ligand displacement reaction and their X‐ray structures feature the exceptional case where both the NC shape and size are fully conserved during the course of ligand exchange. DFT and TD‐DFT calculations allow understanding the bonding and optical properties of clusters 1H–3H. In addition, the reaction of 1H with [Pd(PPh3)2Cl2] in the presence of terminal alkynes led to the formation of new bimetallic Cu−Pd alloy clusters [PdCu14H2{S2P(OnPr)2}6(C≡CR)6] (4: R=Ph; 5: R=C6H4F). [ABSTRACT FROM AUTHOR]

A structural study of ligand exchange on chalcogen‐passivated copper nanoclusters is far less developed. Herein, we report the synthesis of polyhydrido copper nanoclusters [Cu20H11{Se2P(OiBu)2}9] (2) passivated by Se‐donor ligands via ligand replacement reaction on [Cu20H11{S2P(OiPr)2}9] (1) with NH4[Se2P(OiBu)2]. In parallel to the synthesis of 2, cluster [Cu20H11{S2P(CH2CH2Ph)2}9] (4) was produced by the ligand exchange reaction on a new derivative of 1, that is [Cu20H11{S2P(OnPr)2}9] (3). Solid state structures of both clusters 2 and 4 were unequivocally established by single‐crystal X‐ray diffraction studies and cluster 4 epitomizes exceptional case to preserve both the shape and size of the nanocluster during the course of ligand exchange. Structurally precise cluster 2 is the second example where the copper hydride nanocluster is stabilized by Se‐donor ligands. The anatomy of 2 can be visualized as a twisted cuboctahedral Cu13 core, two triangular faces of which are capped by a Cu6 cupola and a single Cu atom along the C3 rotational axis. [ABSTRACT FROM AUTHOR]

Building upon our earlier studies of cobaltaheteroboranes, we explore the chemistry with heavier group 9 metals. Reaction of [Cp*M(µ‐Cl)Clx]2 (Cp* = η5‐C5Me5; M = Co, x = 0; M = Rh or Ir, x = 1) with [LiBH4·THF], followed by thermolysis with an excess of chalcogen powders (S or Se), affords dimetallaheteroboranes nido‐[(Cp*M)2B2H2E2], 1–4 (1: E = S; 2: E = Se, M = Co; 3 and 4: E = Se, M = Rh and Ir, respectively) in moderate‐to‐good yields. The solid‐state structures of these compounds show open‐cage triple‐decker clusters. Attempts to isolate the Te analogue have failed; however, in the case of cobalt, we have isolated an 11 skeletal‐electron‐pair nido‐[(Cp*Co)2B5H5Te2], 5. The X‐ray diffraction structure of 5 shows monocapped square antiprismatic geometry, with two Te atoms in the core. To close the central four‐membered B2E2 open ring of nido‐1 and nido‐2, we have performed a reaction with [Ru3(CO)12], which leads to the formation of closo‐[(Cp*Co){µ‐η5:η5‐B2H2E2M}M{µ‐Ru(CO)4}], 6 and 7 [6: E = S; 7: E = Se; M = Ru(CO)2]. In contrast, the reactions of nido‐2 and nido‐3 with [Fe2(CO)9] result in heterometallic clusters nido‐[(Cp*M)Fe(CO)3B2H2Se2], 8 and 9 (8: M = Co; 9: M = Rh), [(Cp*Co)Fe3(CO)8Se2], 10, and [(Cp*Co)Fe2(CO)7Se], 11. As nido‐8 also contains a four‐membered open ring B2Se2, we have treated this with [Ru3(CO)12], which yields closo‐[(Cp*Co){µ‐η5:η5‐B2H2Se2M}M{µ‐Fe(CO)4}], 12 [M = Ru(CO)2], which is analogous to that of 7. In addition, we have analyzed the divergence in the reactivity of nido‐[(Cp*M)2B2H2E2], 2–4, with the help of density functional theory calculations. [ABSTRACT FROM AUTHOR]

Several early-late heterodimetallaborane clusters have been isolated and structurally characterized through spectroscopic and crystallographic analysis. The thermolysis of [Cp2Zr(BH4)2] (Cp = η5-C5H5) with [Cp*IrB3H9] (Cp* = η5-C5Me5) and [(Cp*Rh)2B2H6] yielded arachno-[(Cp2Zr)(Cp*Ir)B3H9] ( 2) and arachno-[(Cp2Zr)(Cp*Rh)B4H10] ( 4), respectively. In a similar fashion, the reaction of [Cp2Hf(BH4)2] was performed with the same set of group 9 metallaboranes that led to the formation of arachno-[(Cp2Hf)(Cp*M′)B4H10] ( 5: M′ = Ir; 6: M′ = Rh). To the best of our knowledge, 2 is the first structurally characterized pentaborane(11) analogue containing zirconium, while the clusters 5 and 6 are the first examples with Hf in a hexaborane(12) core. The bonding between the Zr atoms and the boron ring was studied computationally by DFT methods, and 2 can be defined as a dimetallic analogue of arachno-B5H11 on the basis of the combined experimental and computational results. [ABSTRACT FROM AUTHOR]

The syntheses and structural characterization of the CS2-metal complexes [(η5-C5Me5M)(η2-S2CH2)(η3-S2CH)] ( 1: M = Mo; 2: M = W), which feature partially and fully reduced CS2, are reported. In addition, the cis and trans isomers of the dimetallic (sulfido)molybdenum complexes [(η5-C5Me5Mo)2(µ-S2CH2S)2] ( 3- cis and 4- trans) are described. The [Mo2S4] cores of 3- cis and 4- trans represent paddlewheel-like arrays. All the new compounds were characterized in solution by mass spectrometry, IR spectroscopy, and 1H and 13C NMR spectroscopy. Their structural architectures were established by X-ray crystallographic analysis. Quantum-chemical calculations by DFT methods on the model compounds 1′- 4′- trans showed good agreement with the experimentally observed structural parameters. The large HOMO-LUMO (HOMO = highest occupied molecular orbital, LUMO = lowest unoccupied molecular orbital) gaps are consistent with the high thermodynamic stabilities of these complexes. Further, the presence of short metal-metal cross-cluster bonds in the X-ray structures of 3- cis and 4- trans is supported by natural bond order (NBO) calculations. [ABSTRACT FROM AUTHOR]

Treatment of [Cp*IrCl2]2 (Cp* = pentamethylcyclopentadienyl) with Li[BH3(SePh)] at room temperature led to the isolation of a dimetala analogue of hexaborane(10), nido-[(Cp*Ir)(µ-SePh)2Ir{(Cp*Ir)SePh}B4H8] ( 1). Solid-state X-ray structure analysis of 1 showed an extended sandwich molecule with two iridium atoms between Cp* and a [B4Ir] ring. Further, in an effort to synthesize the Rh analogue of 1 under similar reaction conditions, we isolated arachno-[{(Cp*Rh)(µ-SePh)3}Rh(µ-SePh)B3H6] ( 2), a rhodium analogue of tetraboarane(10) in which the {RhB3} unit shows geometric equivalence with a metal π-allyl {MC3} species. Ir complex 1, having an Ir-Ir bond, can be considered similar to the dizinc sandwich complex [Cp*Zn-ZnCp*] in terms of the valence electron count at the metal centers. [ABSTRACT FROM AUTHOR]

A combined experimental and quantum-chemical study of a series of homometallic metallaheteroboranes [(Cp*M)2-E6B2H2] (M = Rh or RuH; E = S or Se; Cp* = η5-C5Me5), which are analogues of 1,3-bishomocubane, is reported. The thermolysis of nido-[(Cp*Rh)2B3H7] (1) in the presence of S or Se powder in toluene yielded bishomocubane clusters [(Cp*Rh)2-(μ-E)2(μ3-E)4B2H2], (3: E = S; 4: E = Se). In a similar fashion, the treatment of nido-[(Cp*RuH)2B3H7] (2) with S or Se powder in p-xylene yielded [(Cp*Ru)2(μ-E)2(μ3-E)4B2H2] (5: E = S; 6: E = Se) and [(Cp*Ru)2(μ3-Se)(μ4-Se)B3H5] (7). One of the noteworthy features of 3-6 is the presence of an electronprecise trichalcogenoborato ligand. All of the compounds have been characterized by mass spectrometry; IR spectroscopy; and 1H, 11B, and 13C NMR spectroscopy. The structures of 3, 4, 6, and 7 were established unequivocally by Xray crystallographic analysis. Quantum-chemical calculations by DFT methods for 3, 4, and 6 showed reasonable agreement with the experimentally observed structural parameters. The large HOMO-LUMO gaps are consistent with the high stabilities of these complexes. [ABSTRACT FROM AUTHOR]

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 [B2H6] moiety into the [Re2(CO)10] framework significantly enhances the catalytic activity. Note that [Re2(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. [ABSTRACT FROM AUTHOR]

The synthesis, structural characterization, and reactivity of new bridged borylene complexes are reported. The reaction of [{Cp*CoCl}2] with LiBH4 ⋅THF at −70 °C, followed by treatment with [M(CO)3(MeCN)3] (M=W, Mo, and Cr) under mild conditions, yielded heteronuclear triply bridged borylene complexes, [(μ3-BH)(Cp*Co)2(μ-CO)M(CO)5] ( 1- 3; 1: M=W, 2: M=Mo, 3: M=Cr). During the syntheses of complexes 1- 3, capped-octahedral cluster [(Cp*Co)2(μ-H)(BH)4{Co(CO)2}] ( 4) was also isolated in good yield. Complexes 1- 3 are isoelectronic and isostructural to [(μ3-BH)(Cp*RuCO)2(μ-CO){Fe(CO)3}] ( 5) and [(μ3-BH)(Cp*RuCO)2(μ-H)(μ-CO){Mn(CO)3}] ( 6), with a trigonal-pyramidal geometry in which the μ3-BH ligand occupies the apical vertex. To test the reactivity of these borylene complexes towards bis-phosphine ligands, the room-temperature photolysis of complexes 1- 3, 5, 6, and [{(μ3-BH)(Cp*Ru)Fe(CO)3}2(μ-CO)] ( 7) was carried out. Most of these complexes led to decomposition, although photolysis of complex 7 with [Ph2P(CH2) nPPh2] ( n=1-3) yielded complexes 9- 11, [3,4-(Ph2P(CH2) nPPh2)- closo-1,2,3,4-Ru2Fe2(BH)2] ( 9: n=1, 10: n=2, 11: n=3). Quantum-chemical calculations by using DFT methods were carried out on compounds 1- 3 and 9- 11 and showed reasonable agreement with the experimentally obtained structural parameters, that is, large HOMO-LUMO gaps, in accordance with the high stabilities of these complexes, and NMR chemical shifts that accurately reflected the experimentally observed resonances. All of the new compounds were characterized in solution by using mass spectrometry, IR spectroscopy, and 1H, 13C, and 11B NMR spectroscopy and their structural types were unequivocally established by crystallographic analysis of complexes 1, 2, 4, 9, and 10. [ABSTRACT FROM AUTHOR]