Zwei- und dreikernige Komplexe des WS42– mit Tricarbonylrhenium(I)- und -mangan(I)-Fragmenten: Struktur,Spektroskopie und Elektrochemie

Di- and Trinuclear Complexes of WS₄^2– with Tricarbonylrhenium(I) and -manganese(I) Fragments: Structure, Spectroscopy, and Electrochemistry The reaction of (NEt₄)₂WS₄ with two equivalents of M(CO)₅(O₃SCF₃), M = Mn or Re, in acetonitrile yielded the crystallographically characterized neutral compounds [(CH₃CN)(OC)₃M(μ-S₂WS₂)M(CO)₃(NCCH₃)]. The individual molecules are chiral and contain WS₄ and MS₂(CO)₃(CH₃CN) moieties in approximately tetrahedral and octahedral configurations, respectively. Vibrational and electronic absorption spectra are in agreement with the crystal structure, comparable results were obtained for trinuclear complexes [(L)(OC)₃Re(μ-S₂WS₂)Re(CO)₃(L)](NEt₄)₂, L = Cl^– or CN^–, and for the dinuclear systems [(WS₄)Re(CO)₃(CH₃CN)](NEt₄) and [(WS₄)Re(CO)₃Cl](NEt₄)₂. Electrochemical processes are irreversible due to the lability of acetonitrile or chloride ligands in corresponding complexes, however, the cyanide compound [(NC)(OC)₃Re(μ-S₂WS₂)Re(CO)₃(CN)]^2– showed reversible one-electron reduction to a first tetrathiotungstate(V) species as detected by UV/Vis/IR spectroelectrochemistry.     

Cyanomethyl cyclopentadienyl complexes of cobalt

The reactions of the complexes CpCo(CO)L (Cp = cyclopentadienyl, L = CO, PPh₃) with ClCH₂CN have been investigated. Chloroacetonitrile reacts with CpCo(CO)PPh₃ to give the cationic complex [CpCo(CH₂CN)(CNCH₂Cl)PPh₃]⁺, which has been isolated and characterized. Compounds of the type [CpCo(CH₂CN)(bipy)]⁺ BPh₄^? and CpCo(CH₂CN)PPh₃CN have been obtained by substitution reactions.     

Isolation of fac-[Re(CO)3(HMPA)3][BF4]. Structural characterization of a key cationic intermediate in the exchange reaction between [Re(CO)6][BF4] and acetylferrocene. Implications in radiopharmaceutical chemistry

[Re(CO)₆][BF₄] reacts with HMPA to form [Re(CO)₃(HMPA)₃][BF₄] (4), whose structure was determined by X-ray crystallography and proves to be a key intermediate in the ligand exchange reaction between three CO and Cp; and may be related to other cations such as [Re(CO)₃(H₂O)₃]⁺, [Re(CO)₃(CH₃CN)₃]⁺, [Re(CO)₃(DMSO)₃]⁺, obtained by different ways, and important in the field of organometallic radiopharmaceuticals.     

From Metallaborane to Borylene Complexes: Syntheses and Structures of Triply Bridged Ruthenium and Tantalum Borylene Complexes

Reaction of [1,2‐(Cp*RuH)₂B₃H₇] ( 1 ; Cp*=η⁵‐C₅Me₅) with [Mo(CO)₃(CH₃CN)₃] yielded arachno‐[(Cp*RuCO)₂B₂H₆] ( 2 ), which exhibits a butterfly structure, reminiscent of 7 sep B₄H₁₀. Compound 2 was found to be a very good precursor for the generation of bridged borylene species. Mild pyrolysis of 2 with [Fe₂(CO)₉] yielded a triply bridged heterotrinuclear borylene complex [(μ₃‐BH)(Cp*RuCO)₂(μ‐CO){Fe(CO)₃}] ( 3 ) and bis‐borylene complexes [{(μ₃‐BH)(Cp*Ru)(μ‐CO)}₂Fe₂(CO)₅] ( 4 ) and [{(μ₃‐BH)(Cp*Ru)Fe(CO)₃}₂(μ‐CO)] ( 5 ). In a similar fashion, pyrolysis of 2 with [Mn₂(CO)₁₀] permits the isolation of μ₃‐borylene complex [(μ₃‐BH)(Cp*RuCO)₂(μ‐H)(μ‐CO){Mn(CO)₃}] ( 6 ). Both compounds 3 and 6 have a trigonal‐pyramidal geometry with the μ₃‐BH ligand occupying the apical vertex, whereas 4 and 5 can be viewed as bicapped tetrahedra, with two μ₃‐borylene ligands occupying the capping position. The synthesis of tantalum borylene complex [(μ₃‐BH)(Cp*TaCO)₂(μ‐CO){Fe(CO)₃}] ( 7 ) was achieved by the reaction of [(Cp*Ta)₂B₄H₈(μ‐BH₄)] at ambient temperature with [Fe₂(CO)₉]. Compounds 2 – 7 have been isolated in modest yield as yellow to red crystalline solids. All the new compounds have been characterized in solution by mass spectrometry; IR spectroscopy; and ¹H, ¹¹B, and ¹³C NMR spectroscopy and the structural types were unequivocally established by crystallographic analysis of 2 – 6 .     

Transient Raman detection of excited state electron,transfer to methyl viologen from photoexcited molecular reagents in fluid solution and anchored to SiO2

The lowest electronic excited state of the complexes [Ru(2,2′-bipyridine)₃]²⁺, fac-[ClRe (CO)₃(2,2′-bipyridine)], and fac-[(pyridine) Re (CO)₃(2,2′-bipyridine)]⁺ can be quenched by methyl viologen, MV²⁺, N,N′-dimethyl-4,4′-bipyridinium, in fluid solutions. The quenching obeys Stern—Volmer kinetics as deduced from plots of relative luminescence quantum yield vs [MV²⁺], and the data are consistent with a quenching process that is essentially diffusion controlled. Pulsed laser excitation (18 ns, 354.7 nm frequency tripled Nd: YAG) of the metal complexes in the presence of MV²⁺ shows that a detectable fraction of the quenching results in net electron transfer to form MV⁺. The MV⁺ is detectable by resonance Raman scattering from the trailing portion of the excitation pulse. Excited state electron transfer to MV²⁺ from a photo-excited complex anchored to SiO₂ has also been detected by transient Raman spectroscopy. High surface area SiO₂ was functionalized by reaction with 4-[2-(trimethoxysilyl)ethyl]pyridine to give [SiO₂]-SiEtpyr. Reaction of [SiO₂]-SiEtpyr with [(CH₃CN)Re(CO)₃(2,2′-bipyridine)]⁺ then yields [SiO₂]-[(SiEtpyr) Re (CO)₃ (2,2′-bipyridine)]⁺. Electron transfer quenching of the photo-excited immobilized Re complex occurs when suspended in CH₃CN solutions of MV²⁺ to yield MV⁺ as detected by resonance Raman scattering and by lifetime attenuation in the presence of MV²⁺.     

Facile Access to Transition‐Metal–Carbonyl Complexes with an Amidinate‐Stabilized Chlorosilylene Ligand

Three transition‐metal–carbonyl complexes [V( L )(CO)₃(Cp)] ( 1 ), [Co( L )(CO)(Cp)] ( 2 ), and [Co( L₂ )(CO)₃]⁺[CoCO)₄]^? ( 3 ), each containing stable N‐heterocyclic‐chlorosilylene ligands ( L ; L =PhC(NtBu)₂SiCl) were synthesized from [V(CO)₄(Cp)], [Co(CO)₂(Cp)], and Co₂(CO)₈, respectively. Complexes 1 , 2 , 3 were characterized by NMR and IR spectroscopy, EI‐MS spectrometry, and elemental analysis. The molecular structures of compounds 1 , 2 , 3 were determined by single‐crystal X‐ray diffraction.     

Metal-Rich Metallaboranes: Synthesis,Structure, and Bonding of Heteronuclear Trimetallic Clusters containing (μ3-BH) Ligand

Building upon our earlier results on the chemistry of nido-1,2-[(Cp*RuH)₂B₃H₇] (Cp*=ɳ⁵-C₅Me₅) (nido- 1 ) with different transition metal carbonyls, we continued to investigate the reactivity with group 7 metal carbonyls under photolytic condition. Photolysis of nido- 1 with [Mn₂(CO)₁₀] led to the isolation of a trimetallic [(Cp*Ru)₂{Mn(CO)₃}(μ-H)(μ-CO)₃(μ₃-BH)] ( 2 ) cluster with a triply bridging borylene moiety. Cluster 2 is a rare example of a tetrahedral cluster having hydrido(hydroborylene) moiety. In an attempt to synthesize the Re analogue of 2 , a similar reaction was carried out with [Re₂(CO)₁₀] that yielded the trimetallic [(Cp*Ru)₂{Re(CO)₃}(μ-H)(μ-CO)₃(μ₃-BH)] ( 3 ) cluster having a triply bridging borylene unit. Along with 3 , a trimetallic square pyramid cluster [(Cp*Ru)₂{Re(CO)₃}(μ-H)₂(μ-CO)(μ₃,ɳ²-B₂H₅)] ( 4 ), and heterotrimetallic hydride clusters [{Cp*Ru(CO)₂}-{Re(CO)₄}₂(μ-H)] ( 5 ) and [{Cp*Ru(CO)}{Re(CO)₄}₂(μ-H)₃] ( 6 ) were isolated. Cluster 4 is a unique example of a M₂M′B₂ cluster having diboron capped Ru₂Re-triangle. The hydride clusters 5 and 6 have triangular RuRe₂ frameworks with one and three μ-Hs respectively. All the clusters have been characterized by using mass spectrometry, ¹H, ¹¹B{¹H}, ¹³C{¹H} NMR and IR spectroscopies analyses and the structures of clusters 2 – 6 have been unambiguously established by XRD analyses. Furthermore, to understand the electronic, structural, and bonding features of the synthesized metal-rich clusters, DFT calculations have been performed.     

Addition von kationischen Lewis‐Säuren [M′Ln]+ (M′Ln = Fe(CO)2Cp,Fe(CO)(PPh3)Cp,Ru(PPh3)2Cp,Re(CO)5, ${1 \over 2}$ Pt(PPh3)2, W(CO)3Cp an die anionischen Thiocarbonyl‐Komplexe [HB(pz)3(OC)2M(CS)]− (M = Mo,W; pz = 3,5‐dimethylpyrazol‐1‐yl)

Addition of Cationic Lewis Acids [M′L_n]⁺ (M′L_n = Fe(CO)₂Cp, Fe(CO)(PPh₃)Cp, Ru(PPh₃)₂Cp, Re(CO)₅, Pt(PPh₃)₂, W(CO)₃Cp to the Anionic Thiocarbonyl Complexes [HB(pz)₃(OC)₂M(CS)]⁻ (M = Mo, W; pz = 3,5‐dimethylpyrazol‐1‐yl) Adducts from Organometallic Lewis Acids [Fe(CO)₂Cp]⁺, [Fe(CO)(PPh₃)Cp]⁺, [Ru(PPh₃)₂Cp]⁺, [Re(CO)₅]⁺, [ Pt(PPh₃)₂]⁺, [W(CO)₃Cp]⁺ and the anionic thiocarbonyl complexes [HB(pz)₃(OC)₂M(CS)]⁻ (M = Mo, W) have been prepared. Their spectroscopic data indicate that the addition of the cations occurs at the sulphur atom to give end‐to‐end thiocarbonyl bridged complexes [HB(pz)₃(OC)₂MCSM′L_n].     

New Trinuclear Complexes of Group 6, 8, and 9 Metals with a Triply Bridging Borylene Ligand

Trinuclear complexes of group 6, 8, and 9 transition metals with a (μ₃‐BH) ligand [(μ₃‐BH)(Cp*Rh)₂(μ‐CO)M′(CO)₅], 3 and 4 ( 3 : M′=Mo; 4 : M′=W) and 5 – 8 , [(Cp*Ru)₃(μ₃‐CO)₂(μ₃‐BH)(μ₃‐E)(μ‐H){M′(CO)₃}] ( 5 : M′=Cr, E=CO; 6 : M′=Mo, E=CO; 7 : M′=Mo, E=BH; 8 : M′=W, E=CO), have been synthesized from the reaction between nido‐[(Cp*M)₂B₃H₇] (nido‐ 1 : M=Rh; nido‐ 2 : M=RuH, Cp*=η⁵‐C₅Me₅) and [M′(CO)₅ ? thf] (M′=Mo and W). Compounds 3 and 4 are isoelectronic and isostructural with [(μ₃‐BH)(Cp*Co)₂(μ‐CO)M′(CO)₅], (M′=Cr, Mo and W) and [(μ₃‐BH)(Cp*Co)₂(μ‐CO)(μ‐H)₂M′′H(CO)₃], (M′′=Mn and Re). All compounds are composed of a bridging borylene ligand (B?H) that is effectively stabilized by a trinuclear framework. In contrast, the reaction of nido‐ 1 with [Cr(CO)₅ ? thf] gave [(Cp*Rh)₂Cr(CO)₃(μ‐CO)(μ₃‐BH)(B₂H₄)] ( 9 ). The geometry of 9 can be viewed as a condensed polyhedron composed of [Rh₂Cr(μ₃‐BH)] and [Rh₂CrB₂], a tetrahedral and a square pyramidal geometry, respectively. The bonding of 9 can be considered by using the polyhedral fusion formalism of Mingos. All compounds have been characterized by using different spectroscopic studies and the molecular structures were determined by using single‐crystal X‐ray diffraction analysis.     

A General Pathway to Heterobimetallic Triple-Decker Complexes

A systematic study on the reactivity of the triple-decker complex [(Cp’’’Co)₂(μ,η⁴:η⁴-C₇H₈)] ( A ) (Cp’’’=1,2,4-tritertbutyl-cyclopentadienyl) towards sandwich complexes containing cyclo-P₃, cyclo-P₄, and cyclo-P₅ ligands under mild conditions is presented. The heterobimetallic triple-decker sandwich complexes [(Cp*Fe)(Cp’’’Co)(μ,η⁵:η⁴-P₅)] ( 1 ) and [(Cp’’’Co)(Cp’’’Ni)(μ,η³:η³-P₃)] ( 3 ) (Cp*=1,2,3,4,5-pentamethylcyclopentadienyl) were synthesized and fully characterized. In solution, these complexes exhibit a unique fluxional behavior, which was investigated by variable temperature NMR spectroscopy. The dynamic processes can be blocked by coordination to {W(CO)₅} fragments, leading to the complexes [(Cp*Fe)(Cp’’’Co)(μ₃,η⁵:η⁴:η¹-P₅){W(CO)₅}] ( 2 a ), [(Cp*Fe)(Cp’’’Co)(μ₄,η⁵:η⁴:η¹:η¹-P₅){(W(CO)₅)₂}] ( 2 b ), and [(Cp’’’Co)(Cp’’’Ni)(μ₃,η³:η²:η¹-P₃){W(CO)₅}] ( 4 ), respectively. The thermolysis of 3 leads to the tetrahedrane complex [(Cp’’’Ni)₂(μ,η²:η²-P₂)] ( 5 ). All compounds were fully characterized using single-crystal X-ray structure analysis, NMR spectroscopy, mass spectrometry, and elemental analysis.     

Protonation of Cp(CO)(PPh3) RuCCPh: Formation of cationnic phenylacetylene and phenylvinylidene complexes and subsequent reaction with ethylene oxide to form the net [2 + 3] cycloadduct [Cp(CO)(PPH3)Ru=CCH(Ph)CH2CH2O]+

Protonation of the alkynyl complex Cp(CO)(PPh₃)RuCCPh (1) at low temperature affords quantitatively the vinylidened complex [Cp(CO)(PPh₃)RuCCH(Ph)]⁺ (3), which upon warming to room temperature forms an equilibrium with the η²-phenylacetylene complex [Cp(CO)(PPh₃)Ru(η²-HCCPh)]⁺ (4), with the latter predominating. Subsequent reaction with ethylene oxide yields the cyclic oxacarbene complex [Cp(CO)(PPH₃)Ru=CCH(Ph)CH₂CH₂O]⁺ (5), which can be regarded as the result of a net [3+2] cycloaddition reaction between 3 and ethylene oxide. Depronation of 5 affords teh corresponding neutral cyclic vinyl complex [Cp(CO)(PPH₃)RuC=C(Ph)CH₂CH₂O]⁺ (6), which can in turn be protonated to regenerate 5 in a diastereoselective manner. The structures of complexes 5 and 6 were determined by X-ray crystallography.     

New Heteronuclear Bridged Borylene Complexes That Were Derived from [{Cp*CoCl}2] and Mono‐Metal?Carbonyl Fragments

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 .     

Stereospecific synthesis and redox properties of ruthenium(II) carbonyl complexes bearing a redox-active 1,8-naphthyridine unit

Two stereoisomers of cis-[Ru(bpy)(pynp)(CO)Cl]PF₆ (bpy = 2,2′-bipyridine, pynp = 2-(2-pyridyl)-1,8-naphthyridine) were selectively prepared. The pyridyl rings of the pynp ligand in [Ru(bpy)(pynp)(CO)Cl]⁺ are situated trans and cis, respectively, to the CO ligand. The corresponding CH₃CN complex ([Ru(bpy)(pynp)(CO)(CH₃CN)]²⁺) was also prepared by replacement reactions of the chlorido ligand in CH₃CN. Using these complexes, ligand-centered redox behavior was studied by electrochemical and spectroelectrochemical techniques. The molecular structures of pynp-containing complexes (two stereoisomers of [Ru(bpy)(pynp)(CO)Cl]PF₆ and [Ru(pynp)₂(CO)Cl]PF₆) were determined by X-ray structure analyses.     

Rhenium‐Dicarbonyl‐Nitrosyl‐Komplexe mit Imidazol

Rhenium Dicarbonyl‐Nitrosyl Complexes with Imidazole Different rhenium‐dicarbonyl‐nitrosyl complexes with imidazole (Im) as monodentate ligand have been synthesized and characterized, starting from [NEt₄][ReCl₃(CO)₂(NO)] and [ReCl(μ?Cl)(CO)₂(NO)]₂. Whereas the complexes [ReCl₂(Im)(CO)₂(NO)] and [ReCl(Im)₂(CO)₂(NO)]⁺ were achieved in high yields, the complex [Re(Im)₃(CO)₂(NO)]²⁺ with three imidazole ligands could only be isolated after complete removal of all halide ions (with AgBF₄) in low yield. The synthesis of a corresponding ^99mTc‐dicarbonyl‐nitrosyl complex with imidazole opens a new perspective for such compounds as potential radiopharmaceuticals and alternatives to the already established ^99mTc‐tricarbonyl complexes.     

Vinylidene complexes of transition metals : III. Derivatives of cyclopentadienyltricarbonyl rhenium with phenylvinylidene ligands. Crystal and molecular structure of Cp(CO)2Re[CC(Ph)C(Ph)CH2]Re(CO)2Cp

The novel complexes CpRe(CCHPh)(CO)₂ and Cp₂Re₂(μ-CCHPh)(CO)₄ containing a terminal and a bridging phenylvinylidene ligand respectively and the binuclear complex Cp(CO)₂Re[CC(Ph)C(Ph)CH₂]Re(CO)₂Cp were obtained in the reaction of CpRe(CO)₃ with PhCCH.According to an X-ray study of the latter complex the unusual bridging ligand is η¹-bonded to one Re atom and η²-bonded to the other.     

Exploratory organometal-sulfur chemistry; syntheses and unusual properties of rhenium CH2SR,CHSRR′, and CHSR]+ complexes

The methylidene complex [(η-C₅H₅)Re(NO)(PPh₃)(CH₂)]⁺PF₆^?(I) yields kinetically labile sulfonium salts when treated with CH₃SCH₃, CH₃SCH₂C₆H₅, and (η-C₅H₅)Re(NO)(PPh₃)(CH₂SCH₃) (V);the binuclear adduct formed in the latter case, [(η-C₅H₅)Re(NO)(PPh₃)CH₂]₂S⁺CH₃ (VI), is substantially more stable than the others and undergoes hydride transfer disproportionation to [(η-C₅H₅)Re(NO)(PPh₃)(CHSCH₃)]⁺PF₆^?(VII) and (η-C₅H₅)Re(NO)(PPh₃)(CH₃) (VIII) when heated.     

A perchlorate-promoted electrochemically induced nitride coupling reaction

The osmium nitride complex [Os^VI(NH₃)₄N]³⁺ undergoes a one-electron reduction in acetonitrile to give [Os^V(N)(NH₃)₄]²⁺, which further reacts by nitride coupling to give the μ-dinitrogen osmium complex [(CH₃CN)(NH₃)₄Os^II(N₂)Os^II(NH₃)₄(CH₃CN)]⁴⁺. The formation of the μ-dinitrogen osmium complex is promoted by the presence of perchlorate anion, which causes the deposition of [(CH₃CN)(NH₃)₄Os^II(N₂)Os^II(NH₃)₄(CH₃CN)](ClO₄)₄ on the electrode surface upon repetitive voltammetric scans.     

Synthesis,structure, redox property and ligand replacement reaction of ruthenium(II) complexes containing a terpyridyl ligand with a redox active moiety

Ruthenium(II) complexes bearing a redox-active tridentate ligand 4′-(2,5-dimethoxyphenyl)-2,2′:6′,2′′-terpyridine (tpyOMe), analogous to terpyridine, and 2,2′-bipyridine (bpy) were synthesized by the sequential replacement of Cl by CH₃CN and CO on the complex. The new ruthenium complexes were characterized by various methods including IR and NMR. The molecular structures of [Ru(tpyOMe)(bpy)(CH₃CN)]²⁺ and two kinds of [Ru(tpyOMe)(bpy)(CO)]²⁺ were determined by X-ray crystallography. The incorporation of monodentate ligands (Cl, CH₃CN and CO) regulated the energy levels of the MLCT transitions and the metal-centered redox potentials of the complexes. The kinetic data observed in this study indicates that the ligand replacement reaction of [Ru(tpyOMe)(bpy)Cl]⁺ to [Ru(tpyOMe)(bpy)(CH₃CN)]²⁺ proceeds by a solvent-assisted dissociation process.     

Syntheses and Characterization of New Vinyl‐Borylene Complexes by the Hydroboration of Alkynes with [(μ3‐BH)(Cp*RuCO)2(μ‐CO)Fe(CO)3]

Room temperature photolysis of a triply‐bridged borylene complex, [(μ₃‐BH)(Cp*RuCO)₂(μ‐CO)Fe(CO)₃] ( 1 a ; Cp*=C₅Me₅), in the presence of a series of alkynes, 1,2‐diphenylethyne, 1‐phenyl‐1‐propyne, and 2‐butyne led to the isolation of unprecedented vinyl‐borylene complexes (Z)‐[(Cp*RuCO)₂(μ‐CO)B(CR)(CHR′)] ( 2 : R, R′=Ph; 3 : R=Me, R′=Ph; 4 : R, R′=Me). This reaction permits a hydroboration of alkyne through an anti ‐ Markovnikov addition. In stark contrast, in the presence of phenylacetylene, a metallacarborane, closo‐[1,2‐(Cp*Ru)₂(μ‐CO)₂{Fe₂(CO)₅}‐4‐Ph‐4,5‐C₂BH₂] ( 5 a) , is formed. A plausible mechanism has been proposed for the formation of vinyl‐borylene complexes, which is supported by density functional theory (DFT) methods. Furthermore, the calculated ¹¹B NMR chemical shifts accurately reflect the experimentally measured shifts. All the new compounds have been characterized in solution by mass spectrometry and IR, ¹H, ¹¹B, and ¹³C NMR spectroscopies and the structural types were unequivocally established by crystallographic analysis of 2 , 5 a , and 5 b .