Search

Metallomacrocycles that include several metal ions with the Lewis acid properties are peculiar antipodes of crown ethers (referred to as ‘anticrowns’ in the literature). Recently these architectures have been extensively investigated when searching for efficient and selective anion receptors. In this review, we analyze the data on the molecular and crystal structures of supramolecular complexes of mercury-containing macrocycles (hosts) with anions or neutral nucleophiles (guests). The emphasis is on the identification and systematization of the structure types of complexes in dependence of the guest molecule nature, as well as the macrocycle composition and structure. The factors affecting the selectivity of coordination and competitive ability of various electron donor moieties of guest molecules to binding to the macrocycle are considered. The data in the literature on the nonvalent host – guest and host – host interactions, which are responsible for the formation of molecular complexes and their supramolecular association in crystals, are analyzed. The formulated structural regularities of these coordination compounds with an unusual type of molecular architecture open ways to design directly promising molecular materials on their basis. The bibliography includes 161 references.

Six new complexes [Cd(tpy)(pfb)2] (1, tpy = 2,2′:6′,2″-terpyridine), [Ln2Cd2(tpy)2(pfb)10] (Ln = Eu (2Eu), Tb (2Tb)), [Ln2Cd2(tbtpy)2(pfb)10]·2MeCN (Ln = Eu (3Eu), Tb (3Tb), tbtpy = 4,4′,4″-tri-tert-butyl-2,2′:6′,2″-terpyridine), [Eu2Cd2(tppz)(pfb)10]n (4, tppz = 2,3,5,6-tetra-(pyridin-2-yl)pyrazine) based on pentafluorobenzoic acid (Hpfb) have been prepared and investigated. The effect of tridentate ligands on geometry heterometallic scaffolds synthesized complexes is discussed. The supramolecular crystal structures of the new compounds are stabilized by π-π, C-F···π, C-H···O, C-H...F, F….F interactions. Non-covalent interactions have been studied using Hirschfeld surface analysis. The obtained compounds were characterized by single-crystal and powder X-ray diffraction, luminescence spectroscopy, IR spectroscopy, CHN analysis. Complexes 2Ln and 3Ln exhibit metal-centered photoluminescence, but the presence of ligand luminescence bands indicates incomplete energy transfer from the d-block to the lanthanide ion.

Heteroleptic cadmium(ii) carboxylates with anions of pentafluorobenzoic (pfb), benzoic (bz), and 2-furancarboxylic (fur) acids were prepared by the crystallization from aqueous solutions. The cadmium(ii) pentafluorobenzoate-benzoate complex is structurally similar to the starting compound [Cd(pfb)(H2O)4]n • n(pfb): bz anions are involved in the cationic 1D polymer {[Cd(bz)(H2O)3]n}n+, whereas pfb anions are outer-sphere. The pentafluorobenzoate-2-furan-carboxylate compound [Cd(fur)(pfb)(H2O)2]n•n(H2O) is a 1D coordination polymer. The heteroleptic TbIII complex [Tb2(bz)2(pfb)4(H2O)2(EtOH)2]•2Hbz has a molecular structure. The supramolecular crystal structures of the new compounds are stabilized by non-covalent interactions.

A series of the cadmium and zinc carboxylate complexes with anions of pentafluorobenzoic (HРfbz) and 2,3,4,5-tetrafluorobenzoic (HТfbz) acids and N-donor ligands (1,10-phenanthroline (Phen) and quinoline (Quin)), [Cd(Pfbz)2(Phen)]n (I), [Cd(Рfbz)2(Рhen)2]·2MeCN (II), [Zn(H2O)-(Рfbz)2(Рhen)] (III), [Zn2Cd(Рfbz)6(Рhen)2]⋅2C6H6 (IV), [Cd2(H2O)2(Tfbz)4(Рhen)2] (V), [Cd2-(H2O)2(Tfbz)4(Quin)2] (VI), and [Cd(Tfbz)2(Phen)2]⋅HTfbz (VII), is synthesized. The structures of new complexes I–VII are determined by X-ray diffraction analysis (CIF files CCDC nos. 1871300, 2005461, 2005462, 2005464, 2005466, 2005465, and 2005459, respectively). The majority of the synthesized compounds is typical of intramolecular stacking interactions between the coordinated molecules of the aromatic N-donor ligands and fluorinated substituents of the carboxylate anions. These interactions lead to the formation of unusual compounds, which are different in the cases of pentafluorobenzoates and tetrafluorobenzoates, in particular, coordination polymer I and binuclear complexes V and VI with coordinated water molecules. The synthesized zinc and cadmium compounds differ in structure and composition.

This work presents an approach for the preparation of functional hydrosilanes. The essence of the method is a thiol–ene click reaction on vinyl or allylsilanes. In this case, the Si–H bond in the substrate molecule is not affected. The reaction proceeds with radical (AIBN) or UV initiation with yields close to quantitative. This makes it possible to obtain aliphatic, aromatic, carboxyl and alkoxysilyl derivatives of the corresponding silanes. Crystalline tris(3-(phenylthio)propyl) silane was obtained and characterized for the first time. In the case when the thiol–ene reaction leads to the formation of a three-dimensional network, it was possible to obtain Si–H-containing materials – a transparent monolith and an aerogel with a density of 0.26 g ml−1.

The reactions of Cd(NO3)2 ∙ 4H2O and Eu(NO3)3 ∙ 6H2O with potassium salts of the benzoic acid derivatives and 2,2'-bipyridine (Bipy) in ethanol, under the same synthesis conditions, afford the homo- and heterometallic complexes: [Eu2Cd2(BA)8(NO3)2(Bipy)2] (I, BA is benzoic acid anion), [Ln2Cd2(4-TBA)10(Bipy)2] (Ln = Eu (II), Tb (III); 4-TBA is 4-(trifluoromethyl)benzoic acid anion), [Cd(4-CBA)2(H2O)(Bipy)] (IV, 4-CBA is 4-cyanobenzoic acid anion), [Cd(PFBA)2(H2O)(Bipy)]n (V, PFBA is pentafluorobenzoic acid anion), and [Cd2(4-APFBA)4(Bipy)2] ∙ 4H2O (VI, 4-ATFBA is 4-amino-2,3,5,6-tetrafluorobenzoic acid anion). The structures of new complexes I, II, IV, and VI are determined by X-ray structure analysis (CIF files CCDC nos. 1970348, 1970350, 1970347, and 1970351, respectively). The isostructural character of complexes II and III is confirmed by X-ray diffraction analysis. The structures and compositions of the series of isolated compounds I–VI are determined by the nature of substituents in the benzoate anion. The photoluminescence properties of compounds II and III are studied.

Crystals of glycinium dicitratoborate monohydrate H3NCH2COOH[B(C6H6O7)2] · Н2О have been synthesized and selected for the first time. Their structure is determined by X-ray diffraction analysis: triclinic system, sp. gr. Р$$\bar {1}$$, and Z = 2. The crystals consist of cation–anion layers, in which all structural units (dicitratoborate anion, glycinium cation, and crystallization-water molecule) are bound firmly by numerous hydrogen bonds.

New trinuclear Cd–Ln molecular complexes [EuCd2(O2CC6F5)6(NO3)(Bipy)2] (I, Bipy is 2,2'-bipyridine) and [LnCd2(Bzo)6(NO3)(Phen)2] · 4MeCN (Ln = Tb (II), Eu (III), Bzo is anion of 3,5-di-tert-butylbenzoic acid, Phen is 1,10-phenanthroline) are studied. Their structures are determined by X-ray structure analysis (СIF files CCDC nos. 1938125 (I), 1938124 (II)) or by X-ray diffraction analysis (III), and the photoluminescence properties are studied. The reactions of complexes I and II with terephthalic acid (H2Bdc) are accompanied by the destruction of the heterometallic molecules to form 2D coordination polymers [Cd3(Bbdc)3(Bipy)2]3n · 4nMeCN · nH2O (IV) and [Cd2(Bdc)2(Phen)2]n · 2nDMF (V) (СIF files CCDC nos. 1938126 and 1937492, respectively).

The effect of methyl substituents in the lower belt of dicarbollide ligands on the redox potential of ruthenacarboranes based thereof, as well as the ability of the metallacarboranes obtained to catalyze radical polymerization with atom transfer were studied. For this purpose, a new approach to the synthesis of closo-ruthenacarboranes based on substituted dicarbollide ligands was developed and six new complexes 3,3-(Ph2P(CH2)4PPh2)-3-H-3-Cl-9-Me-12-X-closo-3,1,2-RuC2B9H9, 3,3,8-(Ph2P(CH2)4PPh-μ-(C6H4-o))-3-Cl-9-Me-12-X-closo-3,1,2-RuC2B9H8 and 3,3,4,8-(Ph2P(CH2)4P-μ-(C6H4-o)2)-3-Cl-9-Me-9-X-closo-3,1,2-RuC2B9H7 (X = H, Me) were synthetized and characterized by single crystal X-ray diffraction, NMR and ESR spectroscopy and MALDI TOF mass-spectrometry. Comparison of the values of the redox potentials of the synthesized ruthenium complexes in 1,2-dichloroethane with the values previously found for the corresponding ruthenacarboranes based on the parent dicarbollide anion showed that the introduction of methyl substituents into the carborane cage led to a decrease in the redox potentials of the complexes, which made them more preferable catalysts for ATRP. Test experiments on the polymerization of MMA showed that the synthesized ruthenacarboranes were effective catalysts for ATRP, the most active being the complex with two methyl groups and two ortho-phenylenecycloboronated fragments.

The reaction between 1,3-bis(diphenylphosphinite)-benzene and Os3(CO)10(MeCN)2 affords complex Os3(CO)10[1,3-(PhPO)2C6H4]. A thermolysis of this cluster in refluxing toluene results in the activation of O–PPh2 and C–H bonds and the formation of unsaturated triosmium cluster Os3(μ-H)(μ-PPh2)(CO)7[(C6H3(O)(OPPh2)] that possesses a remarkable structure with the pseudo-pincer ligand containing a bridging μ-η1-aryl group.

The interaction of the three-mercury anticrown (o-C6F4Hg)3 (1) with various azacrowns such as 2,9,16,23-tetra-tert-butylphthalocyanine (TBPC), octaazapentacyclooctacosane (OAOC), 1,4,8,11-tetraazacyclotetradecane (cyclam), and N,N,N-trimethyl-1,3,5-triazacyclohexane (TACH) has been studied. It has been shown that the reaction of 1 with TBPC in CH2Cl2 at 20 °C affords 1:1 complex {[(o-C6F4Hg)3](TBPC)} (2) according to elemental analysis, and the interaction of 1 with OAOC·0.5H2O in ether results in the formation of complex {[(o-C6F4Hg)3]2(OAOC)(H2O)2} (3). The molecules of azacrown and water in 3 are located between the parallel planes of two mercuramacrocycles strongly laterally shifted relative to one another and are bonded to them through Hg–N and Hg–O secondary interactions. An especially interesting complex, [(CH2)10(NH2)2(NH)2]{[(o-C6F4Hg)3]2Cl2} (4), has been obtained by the reaction of 1 with cyclam [(CH2)10(NH)4] in CH2Cl2 at 20 °C. The complex has a structure of a double-decker sandwich wherein t...

Ferrocenium hexafluorophosphate reacts with aminophosphines P(NEt2)3, PhP(NEt2)2, Ph2P(NEt2), CyP(NEt2)2, and Pri2P(NEt2) to form ferrocenylphosphonium salts [(C5H5)-Fe(C5H4PRR′R″)](PF6), ferrocene, and [HPRR′R″](PF6). The theoretical analysis of the reactions (M06-L/6-311++G(d,p)) showed that these reactions involve a sequence of the following steps: the addition of phosphine to the cyclopentadienyl ring, the oxidation of the initial adduct by the starting ferrocenium to give a dicationic η4-phosphocyclopentadiene complex with an agostic $$C_{sp^{3}}-H\rightarrow{Fe}$$ bond, and the deprotonation of this bond to form ferrocenylphosphonium salts. The resulting ferrocenylphosphonium salts are resistant to alcoholysis and do not react with carbon disulfide.

The crystal structures of PhMeTeI2 (1), FcMeTeI2 (2) and [FcMe2Te]+I− (3), which are the products of iodomethylation of R2Te2 (R = Ph, ferrocenyl (Fc)) by MeI, are reported. Analysis of secondary interactions and packing patterns in 1–3 revealed Te⋯πPh chalcogen bonding in 1, unusual structural parallels between 2 and 3, and unprecedented isomorphic substitution in the crystals of 3 with an admixture of Te–I ionized molecules 2 [FcMeTeI+]I−. In summary, we are discussing the 3c-4e bonding model as a general, seamless scheme for the geometry and electronic structure of hypervalent tellurium atom coordination in both the isolated molecules and crystals, which overcomes the confusing division between the molecular and supramolecular geometry.

Two novel ruthenocene-based pincer palladium tetrahydroborates were characterized by XRD, NMR and FTIR. The alcoholysis of Pd(ii) tetrahydroborate LPd(BH4) (L = κ3-[{2,5-(tBu2PCH2)2C5H2}Ru(C5H5)]) yields the dinuclear cationic Pd(ii) tetrahydroborate with the bridging BH4- ligand [(LPd)2(μ,η1,2:η1,2-BH4)]+. The bifurcate dihydrogen-bonded complexes are the active intermediates of the first proton transfer in the step-wise alcoholysis of LPd(BH4), yielding eventually [(LPd)2(μ,η1,2:η1,2-BH4)]+. According to the X-ray and DFT/M06 geometry analysis, the BH4- ligand in both palladium tetrahydroborates has a mixed coordination mode η1,2. The possibility of BH3-group abstraction from LPd(BH4) by an excess of organic base (THF, Py) with the formation of hydride LPdIIH is shown. This Pd(ii) hydride is a very reactive compound able to rapidly capture CO2 (ca. 15 min) converting into the formate complex LPdII(η1-OC(O)H). The hydrolysis of LPdH with subsequent CO2 insertion yields a hydrocarbonate complex LPdII(η1-OC(O)OH). The hydrocarbonate complex forms hydrogen-bonded dimers in the crystal due to hydrogen bonds between the OC(O)OH fragments.

We report comprehensive X-ray diffraction and NMR studies of potassium-induced dimerization of heteroleptic triple-decker crown-phthalocyaninates [(15C5)4Pc]M(Pc)M(Pc) (1M, M = Y and Tb). Characterization of the crystalline dimer 2(1Y)·4KBPh4·12CH3CN·10CHCl3 gave the first structural evidence of the formation of a six-decker structure with four rare earth metal ions perfectly aligned near the symmetry axis. NMR studies of soluble supramolecular dimers 2(1M)·4KOAc provided a spectral-structural model that allowed us to assign the NMR spectra of related complexes with paramagnetic lanthanides and to further evaluate their structure and long-range interaction between the Ln(III) centers in multinuclear tetrapyrrolic complexes. The obtained results are promising for elaboration of new supramolecular magnetic materials.

This study presents the synthesis of organoboron derivatives of stereoregular 4-, 6-, and 12-unit phenylcyclosilsesquioxanes. All compounds obtained were isolated in good yields (70-80 %) and were fully characterized by 1 H, 13 C, 29 Si, 11 B NMR, IR spectroscopy, HRMS ESI, and elemental microanalysis. The structure of the key modifier, obtained for the first time, 4-(tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl) dimethylvinylsilane, was also confirmed by single-crystal XRD.

The possibility of the partial or complete substitution of the outer-sphere solvate shell of n-butanol molecules by the nitrogen-containing compounds in the phenylnickelsodiumsiloxane complex. The high-symmetry spatially fixed rigidly cationic layer retains its structure. The obtained complexes Na2(μ-H2O)2(n-BuOH)2{[C6H5SiO2]6Ni4Na4(μ3-OH)2[C6H5SiO2]6} · 8(n-BuOH) · 2NH3 (II) and {[C6H5SiO2]6Ni4Na6(μ3-OH)2[C6H5SiO2]6} · 4(μ-C3H7NO) · 6(C3H7NO) · 2.8(H2O) · 0.6(C3H7NO) (III) are studied by X-ray diffraction analysis (CIF files CCDC nos. 1810736 (II) and 1810737 (III)).

The thermally and photochemically activated reactions of Ru3(CO)12 with 4-dimethylaminobut-3-en-2-one (L) were studied and several mononuclear and polynuclear products were isolated and fully characterized by a combination of spectroscopic IR and multinuclear NMR data as well by single-crystal X-ray diffraction studies. Chelate five-membered oxaruthenacycles found to be present in all the isolated organometallic products are formed via Cβ H activation reactions. These metallacycles can be bound to other ruthenium atoms in the different modes, namely, through π-coordination to the olefinic bond, through σ-coordination to the Cα atom of the starting ligand, and by coordination through the lone pair of the oxygen atom. The coordination of a metal atom to the Cα atom caused by an isomerization of the ligand to form partially imine C N bond and migration of the olefinic bond has not been observed previously in reactions of Ru3(CO)12 with oxadienes. The formation of the six-membered chelate azaoxaruthenacycles in the reaction with L is accompanied by a migration and reduction of the olefinic bond. These chelates are significantly less stable than the five-membered chelates and involved coordination to other metal atoms to form polynuclear products. The structural and spectroscopic features and possible transformations pathways of the resulting complexes are discussed.

New monothiolate ruthenium alkylidene complexes bearing bulky tricyclic N-heterocyclic carbene ligands decorated with two geminal trifluoromethyl groups were synthesized. Their catalytic activity in representative olefin metathesis reactions, such as ring closing metathesis of diallyltosylamine and selfmetathesis of allylbenzene, has been evaluated.

A series of new osmacarborane complexes were synthesized by treatment of the 11-vertex carborane [closo-СВ10Н11]–[Me4N]+ (1) with tris(triphenylphosphine)osmiumdichloride OsCl2(PPh3)3 (2). We managed to control the process of the carborane framework transformation {closo-CB10} → {hypercloso-OsCB10} → {hypercloso-OsCB9} → {hypercloso-OsCB8}, and each stage of this polyhedral carborane contraction was experimentally confirmed. The isolated clusters are electron-deficient hypercloso-osmacarboranes with 2n skeletal electrons. The structures of two “anti-Wade” complexes (10- and 11-vertex osmacarboranes) were confirmed by X-ray diffraction.

Anovel facile way of synthesis of closo-ruthenacarboranes with chelate 1,2-bis(diphenylphosphino)ethane (dppe) with high yields was proposed. It was found that the interaction of the three-bridged 5,6,10-{Cl(Ph3P)2Ru}-[5,6,10-(μ-H)3-10-H-exo-nido-7,8-C2B9H10] (1) with dppe in acetonitrile or CH2Cl2/acetonitrile mixture leads to the formation of novel diamagnetic ruthenacarborane cluster 3-СNMe-3,3-[κ2-dppe]-closo-3,1,2-RuC2B9H11 (2) along with some amount of ionic compound [trans-(CH3CN)RuCl(dppe)2]+[C2B9H12]− (3) which may be also converted to 2 increasing its total yield. The reaction of 2 bearing divalent ruthenium with carbon tetrachloride or HCl gives the known 17-electron paramagnetic complex 3-Сl-3,3-[κ2-dppe]-closo-3,1,2-RuC2B9H11 (4)..The detailed investigation of the previously described method of synthesis of 4 from 3-H-3Cl-3,3-(PPh3)2-closo-3,1,2-RuC2B9H11 (5) allowed us to characterize the forming by-products as 3-PPh3-3,3,8-(Ph2P(CH2)2PPh-μ-(C6[H4-о)-closo-3,1,2-RuC2B9]H10 (6) and 3-[κ1-dppe]-3,3-[κ2-dppe]-closo-3,1,2-RuC2B9H11 (7). The obtained ruthenacarborane clusters undergo reversible Ru(II)/Ru(III) transition. It was shown that the complexes 2, 4 and 6 show good activity as catalysts for Atom Transfer Radical Polymerization of methyl methacrylate.

The interaction of copper(I) and silver(I) macrocyclic pyrazolates with aromatic ligands of ruthenium sandwiches (Cp*RuInd, CpRuInd, and Ind2Ru) in solution is shown for the first time. The similar mode of coordination of macrocycles to the C6 fragment of indenyl ligand was found both in the solution and in the solid state. Complexation of macrocycles with the nonencumbered sandwiches (CpRuInd, Ind2Ru) leads to the formation of infinite stacks via alternating molecules of macrocycles and sandwich compounds as one-dimensional coordination polymers with a regular structure. Coordination mode of the indenyl ligand is independent of the second part of the ruthenium sandwich as well as of the aromatic ligand coordinated to another face of the macrocycle. The general principle of macrocycle supramolecular packing suggests coordination of two ligands on both faces of the macrocycle.

The reaction of [Na][C2B8H11] with anhydrous FeCl2 in THF affords a mixture of DD/LL and MESO isomers of anionic paramagnetic commo-ferracarborane [Ph3PR][commo-1,1′-Fe(closo-2,4-C2B8H10)2] (MESO, R = Me: 1a; MESO, Et: 1b; DD/LL, R = Me: 2a; DD/LL, R = Et: 2b) with unusual closo geometry. Both: DD/LL and MESO isomers were successfully isolated and their structures were determined using X-Ray diffraction studies. Paramagnetic properties were confirmed with EPR-spectra as well as oxidative-reductive properties were investigated using cyclic voltammetry. It was shown that facile DD/LL → MESO and MESO → DD/LL transformation leading to equilibrium in CH2Cl2 solution occurs. Quantum chemical calculations of the isomer-to-isomer transformations were performed. Ferra-copper zwitterionic complexes [3,3′,6,7′-exo-{Ph3PCu}-3,3′,6,7′-(µ-H)4-commo-1,1′-Fe(2,4-C2B8H8)2] and [3,3′,6,6′-exo-{Ph3PCu}-3,3′,6,6′-(µ-H)4-commo-1,1′-Fe(2,4-C2B8H8)2] were synthesized and their structures were determined by X-Ray diffraction studies.

The paper reports that the interaction of o,o′-dilithiooctafluorobiphenyl with HgCl2 in ether results in the formation of the lithium chloride complex Li{[(o,o′-C6F4C6F4Hg)4]Cl} (11) of the four-mercury anticrown (o,o′-C6F4C6F4Hg)4 (12) along with the earlier isolated and characterized three-mercury anticrown (o,o′-C6F4C6F4Hg)3 (2). The complex was identified by the reaction with 12-crown-4 and determination of the structure of the [Li(12-crown-4)2]{[(o,o′-C6F4C6F4Hg)4]Cl} (13) formed. According to an X-ray analysis, the chloride anion in 13 is simultaneously coordinated with all four Hg centers of the anticrown, forming with them a pyramidal Hg4Cl fragment. The reaction of 11 (in the form of an acetonitrile solvate, 11·nMeCN) with boiling water leads to removal of LiCl from 11 and to the formation of free anticrown 12, the subsequent recrystallization of which from o-xylene affords the o-xylene complex {[(o,o′-C6F4C6F4Hg)4](o-Me2C6H4)2} (14). The obtained 14 forms in the crystal infinite chains consistin...

The synthesis of new quinazoline derivatives with 2,3- and 4-positioned cymantrenyl fragment is described. Alkylation of 2-substituted quinazolin-4-ones with cymantrenylalkyl bromides on using K2CO3, potassium tert-butoxide, and sodium hydride as bases has been studied. It is established for the first time that condensation of 2-methylquinazolin-4-ones with aldehydes can cause elimination of the substituent at the nitrogen atom in position 3. The new cymantrene derivatives possess fluorescence properties.

The reaction of Cp(CO)2FeI with 2-ethynylpyridine under Sonogashira conditions [5% PdCl2(PPh3)2, 10% CuI, THF–NEt3(2:1)] afforded the title binuclear μ-pyridylvinylidene FePd complex (FePd1) as a benzene solvate, [FePd(C5H5)(C7H5N)I(CO)2]·C6H6, in a very low yield rather than the expected irono-pyridylethynyl complex Cp(CO)2Fe—C[triple-bond]C-(2-C5H4N). The Fe and Pd atoms inFePd1are bridged by carbonyl and pyridylvinylidene ligands, the pyridyl N atom being bonded to the palladium atom. The use of equimolar amounts of PdCl2increases the yield ofFePd1to 12%. The reaction pathway leading toFePd1is proposed.

New all-cis-tetra(p-tolyl)cyclotetrasiloxanetetraol and its derivatives with Si(CH = CH2)Me and Si(H)Me2 groups have been prepared and characterized by IR and NMR spectroscopy, GPC, mass spectrometry, TGA and DSC. Molecular and crystalline structures of the tetraol and its derivative with four Si(CH = CH2)Me groups have been determined by single-crystal X-ray diffraction.

In the reaction of the ionic complex of manganese based on 5,6-dicarba-nido-decaborane [1,1,1-(CO)3-isonido-1,2,4-MnC2B8H10]- tmdaH± (1) (tmdaH+- protonated form of N,N,N′,N′-tetramethyl-1,8-diaminonaphthalene) with triphenylphosphine (PPh3) in the presence of boron trifluoride etherate (BF3⋅Et2O) in benzene, the neutral complex 1,1,1-(CO)3–7-PPh3-isonido-1,2,4-MnC2B8H9 (2) was isolated as one of the main products. The position of the PPh3 substituent in the carborane ligand was established by 1H, 11B, 31P, 13C, [11B−11B]-COSY, 1H{11B} NMR spectroscopy methods and confirmed by X-ray diffraction analysis.