Synthesis, reactivity, and DFT studies of tantalum complexes incorporating diamido-N-heterocyclic carbene ligands. Facile endocyclic C-H bond activation

The syntheses of tantalum derivatives with the potentially tridentate diamido-N-heterocyclic carbene (NHC) ligand are described. Aminolysis and alkane elimination reactions with the diamine-NHC ligands, (Ar)[NCN]H(2) (where (Ar)[NCN]H(2) = (ArNHCH(2)CH(2))(2)(C(3)N(2)); Ar = Mes, p-Tol), provided complexes with a bidentate amide-amine donor configuration. Attempts to promote coordination of the remaining pendent amine donor were unsuccessful. Metathesis reactions with the dilithiated diamido-NHC ligand ((Ar)[NCN]Li(2)) and various Cl(x)Ta(NR'(2))(5-)(x) precursors were successful and generated the desired octahedral (Ar)[NCN]TaCl(x)(NR'(2))(3-)(x) complexes. Attempts to prepare trialkyl tantalum complexes by this methodology resulted in the formation of an unusual metallaaziridine derivative. DFT calculations on model complexes show that the strained metallaaziridine ring forms because it allows the remaining substituents to adopt preferable bonding positions. The calculations predict that the lowest energy pathway involves a tantalum alkylidene intermediate, which undergoes C-H bond activation alpha to the amido to form the metallaaziridine moiety. This mechanism was confirmed by examining the distribution of deuterium atoms in an experiment between (Mes)[NCN]Li(2) and Cl(2)Ta(CD(2)Ph)(3). The single-crystal X-ray structures of (p)(-Tol)[NCNH]Ta(NMe(2))(4) (3), (Mes)[NCNH]Ta=CHPh(CH(2)Ph)(2) (4), (p)(-Tol)[NCN]Ta(NMe(2))(3) (7), (Mes)[NCCN]Ta(CH(2)(t)Bu)(2) (11), and (Mes)[NCCN]TaCl(CH(2)(t)Bu) (14) are included.     

Supramolecular silanol chemistry in the gas phase. Topological (AIM) and population (NBO) analyses of hydrogen-bonded complexes between H3SiOH and selected O- and N-acceptor molecules

Hydrogen bonding of the type SiO-H...A (A = O, N) has been studied in the gas phase for simple H3SiOH.acceptor complexes with the acceptor molecules being O(H)SiH3, OH2, O(H)CH3, O(CH3)2, O(CH3)SiH3, O(SiH3)2, NH3, N(CH3)H2, N(CH3)2H, N(CH3)3, N(CH3)2C6H5, and NC5H5, respectively, at the B3LYP/6-311+(2d,p) level of theory, using Bader's atoms in molecules (AIM) and Weinhold's natural bond orbital (NBO) methodology. For all complexes (except H3SiOH.N(CH3)2C6H5) the complex energy Eadd. is a good estimate for the hydrogen bond energy EHB, which is generally higher in N-acceptor complexes (-5.52 to -7.17 kcal mol-1) than in O-acceptor complexes (-2.09 to -5.06 kcal mol-1). In case of H3SiOH.N(CH3)2C6H5, EHB and Eadd. differ by the energy associated with the loss of n(N)-->pi conjugation in N(CH3)2C6H5 upon complex formation. EHB shows no correlation with O...A distances and the red shifts Deltanu(OH) of the OH-stretching vibrations when different acceptors are compared, although both parameters are commonly used to estimate the strength of the hydrogen bond from spectroscopic and diffraction data. A good linear correlation of the hydrogen bond energy EHB has been established with parameters derived from the AIM and NBO analyses, namely, the electron densities rho(HA) and rho(OH) at the H...A and O-H bond critical points (BCPs) and the NLMO bond orders BONLMO(HA) of the H...A bonds of the H3SiOH.acceptor complexes as well as the change of natural charges DeltaqNPA(O) at the O-donor atom upon H3SiOH.acceptor complex formation. Hydrogen bonding of the type SiO-H...A (A = O, N) has been also studied in the related cyclic multiple H3SiOH.acceptor complexes (H3SiOH)3, (H3SiOH)2.NC5H5, and (H3SiOH)4, respectively, at the same level of theory. Cooperative hydrogen bonding is evident for all cyclic multiple H3SiOH.acceptor complexes, whereby the strongest concomitant strengthening of the hydrogen bonds is observed for (H3SiOH)4 and (H3SiOH)2.NC5H5.     

Hydride transfer reactivity of tetrakis(trimethylphosphine)(hydrido)(nitrosyl)molybdenum(0)

The tetrakis(trimethylphosphine) molybdenum nitrosyl hydrido complex trans-Mo(PMe(3))(4)(H)(NO) (2) and the related deuteride complex trans-Mo(PMe(3))(4)(D)(NO) (2a) were prepared from trans-Mo(PMe(3))(4)(Cl)(NO) (1). From (2)H T(1 min) measurements and solid-state (2)H NMR the bond ionicities of 2a could be determined and were found to be 80.0% and 75.3%, respectively, indicating a very polar Mo--D bond. The enhanced hydridicity of 2 is reflected in its very high propensity to undergo hydride transfer reactions. 2 was thus reacted with acetone, acetophenone, and benzophenone to afford the corresponding alkoxide complexes trans-Mo(NO)(PMe(3))(4)(OCHR'R') (R' = R' = Me (3); R' = Me, R' = Ph (4); R' = R' = Ph (5)). The reaction of 2 with CO(2) led to the formation of the formato-O-complex Mo(NO)(OCHO)(PMe(3))(4) (6). The reaction of with HOSO(2)CF(3) produced the anion coordinated complex Mo(NO)(PMe(3))(4)(OSO(2)CF(3)) (7), and the reaction with [H(Et(2)O)(2)][BAr(F)(4)] with an excess of PMe(3) produced the pentakis(trimethylphosphine) coordinated compound [Mo(NO)(PMe(3))(5)][BAr(F)(4)] (8). Imine insertions into the Mo-H bond of 2 were also accomplished. PhCH[double bond, length as m-dash]NPh (N-benzylideneaniline) and C(10)H(7)CH=NPh (N-1-naphthylideneaniline) afforded the amido compounds Mo(NO)(PMe(3))(4)[NR'(CH(2)R')] (R' = R' = Ph (9), R' = Ph, R' = naphthyl (11)). 9 could not be obtained in pure form, however, its structure was assigned by spectroscopic means. At room temperature 11 reacted further to lose one PMe(3) forming 12 (Mo(NO)PMe(3))(3)[N(Ph)CH(2)C(10)H(6))]) with agostic stabilization. In a subsequent step oxidative addition of the agostic naphthyl C-H bond to the molybdenum centre occurred. Then hydrogen migration took place giving the chelate amine complex Mo(NO)(PMe(3))(3)[NH(Ph)(CH(2)C(10)H(6))] (15). The insertion reaction of 2 with C(10)H(7)N=CHPh led to formation of the agostic compound Mo(NO)(PMe(3))(3)[N(CH(2)Ph)(C(10)H(7))] (10). Based on the knowledge of facile formation of agostic compounds the catalytic hydrogenation of C(10)H(7)N=CHPh and PhN=CHC(10)H(7) with 2 (5 mol%) was tested. The best conversion rates were obtained in the presence of an excess of PMe(3), which were 18.4% and 100% for C(10)H(7)N=CHPh and PhN=CHC(10)H(7), respectively.     

Theoretical study of the intermolecular hydrogen bond interaction for furan-HCl and furan-CHCl_3 complexes

The importance of intermolecular interactions in biology and material science has prompted chemists to explore the nature of the variety of such interactions. The strongest of these interac-tions are the hydrogen bonds, which play an important role in determining the molecular confor-mation, crystal packing, and the structure of biological systems such as nucleic acids. Extensive experimental and theoretical efforts[1—5] have been devoted to the studies of this type of interac-tions, such as …     

单电子卤键复合体系H3C···Br-Y(Y=H, CN, NC, CCH, C2H3)的作用机制

对单电子溴键复合物H₃C···Br—Y(Y=H, CCH, CN, NC, C2H3)的结构与性质进行了理论研究. 在B3LYP/6-311++G**水平上计算了稳定构型并做了频率分析. BSSE矫正的相互作用能(E^BSSE)和NBO及AIM分析输入的波函数在MP2/6-311++G**水平下完成. 复合物H₃C···Br—Y中, CH₃(供电子体)自由基均提供一未成对电子与Br—Y中Br(受电子体)形成了单电子溴键, 此单电子溴键也具有“三电子”键的特征. 单电子溴键的形成导致甲基H的背向Y弯曲和Br—Y键的拉长及红移单电子溴键复合物的产生. 考察了电子受体中不同取代基, C(spⁿ)-Br杂化及溶剂的存在对复合物作用的影响, 将单电子氢键, 单电子卤键和单电子锂键的作用强度做了对比, 进一步对Popelier提出的氢键体系中的前三个重要拓扑指标在单电子溴键体系中的重现性进行了探讨.     

CH3SH…HOO开壳型氢键复合物的结构及其电子密度拓扑性质

在DFT-B3LYP/6-311++G**水平下求得CH3SH…HOO复合物势能面上的稳定构型. 计算结果表明, 在HOO以其O8—H7作为质子供体与CH3SH分子中的S5原子为质子受体形成的氢键复合物1和2中, O8—H7明显被“拉长”, 且其伸缩振动频率发生显著的红移, 红移值分别为330.1和320.4 cm-1; 在CH3SH分子以其S5—H6作为质子供体与HOO的端基O9原子为质子受体形成的氢键复合物3和4中, 也存在类似的情况, 但S5—H6伸缩振动频率红移不大. 经MP2/6-311++G**水平计算的4种复合物含BSSE校正的相互作用能分别为-20.81, -20.10, -4.46和-4.52 kJ/mol. 自然键轨道理论(NBO)分析表明, 在CH3SH…HOO复合物1和2中, 引起H7—O8键长增加的因素包括两种电荷转移, 即孤对电子n1(S5)→σ*(H7—O8)和孤对电子n2(S5)→σ*(H7—O8), 其中后者为主要作用. 在复合物3和4中也有相似的电荷转移情况, 但轨道间的相互作用要弱一些. AIM理论分析结果表明, 4个复合物中的S5…H7间和O9…H6间都存在键鞍点, 且其Laplacian量▽2ρ(r)都是很小的正值, 说明这种相互作用介于共价键和离子键之间, 偏静电作用为主.     

Interdependence of redox state,hydrogen bonding,anion recognition and charge partition in crystals of (EDT-TTF-CONHMe)6 [Re6Se8(CN)6] (CH3CN)2(CH2Cl2)2

Neutral pi-conjugated molecules and their radical cations co-exist in [(EDT-TTF-CONHMe+*)4(EDT-TTF-CONHMe0)2] [Re6Se8(CN)6]4- (CH3CN)2(CH2Cl2)2 whose crystal structure reveals that, upon one-electron oxidation, an activation of the N-H and C-H hydrogen bond donor ability is coupled to a deactivation of the hydrogen bond acceptor character of the carbonyl oxygen atom: this is expressed in the supramolecular hydrogen bond pattern and, ultimately, into charge localisation and partition in the solid state.     

Matrix isolation infrared spectroscopic and theoretical study of the reactions of tantalum oxide molecules with methanol

The reactions of tantalum monoxide (TaO) and dioxide (TaO(2)) molecules with methanol in solid neon were investigated by infrared absorption spectroscopy. The ground-state TaO molecule reacted with CH(3)OH in forming the CH(3)OTa(O)H molecule via the hydroxylic hydrogen atom transfer from methanol to the metal center spontaneously on annealing. The observation of the spontaneous reaction is consistent with theoretical predictions that the OH bond activation process is both thermodynamically exothermic and kinetically facile. In contrast, the TaO(2) molecule reacted with CH(3)OH to give primarily the TaO(2)(CH(3)OH) complex, which further rearranged to the CH(3)OTa(O)OH isomer via the hydroxylic hydrogen atom transfer from methanol to one of oxygen atom of metal dioxide upon visible light excitation.     

Solvent-stabilized alkylrhodium(III) hydride complexes: a special mode of reversible C-H bond elimination involving an agostic intermediate

Reaction of the complex [Rh(coe)2(solv)n]BF4 (coe=cyclooctene) with the phosphane 1-di-tert-butylphosphinomethyl-2,4,6-trimethylbenzene (1) results in selective C-H bond activation, yielding the spectroscopically characterized solvento complexes [(solv)nRhH(CH2C6H2(CH3)2[CH2P(tBu)2]]]BF4 (solv = acetone, 2a; THF, 2b; methanol, 2c). The stability of these complexes is solvent dependent, alcohols providing significant stabilization. Although cis-alkylrhodium hydride complexes containing labile ligands are generally unstable, 2a-c are stable at room temperature. Complex [ (acetone)(ketol)RhH[CH2C6H2(CH3)2[CH2P(t-Bu)2]]]BF4 (2d, ketol 4-hydroxy-4-methyl-2-pentanone, the product of acetone aldol condensation), crystallized from a solution of 2a in acetone and was structurally characterized. Unusual solvent- and temperature-dependent selectivity in reversible C-H bond elimination of these complexes, most probably controlled by a special mode of strong agostic interactions, is observed by spin saturation transfer experiments.     

Theoretical study of the intermolecular hydrogen bond interaction for furan-HCl and furan-CHCl<Subscript>3</Subscript> complexes

The nature of the intermolecular hydrogen bond for the furan-HCl and furan-CHCI₃ complexes has been studied using ab initio calculations with MP2 level of theory. The new hydrogen bond type of C(CI)-H...O and π interactions are studied also. It is shown that, for the optimized geometries of furan-CHCI₃, C-H bond lengths contract and vibrational frequencies are blue-shifted, while for the furan-HCl complex, H-CI bond lengths elongate and vibrational frequencies are red-shifted. In addition, the NBO analysis indicates that, for the furan-CHCI₃ complex, the charge transfers from the lone pair of the proton acceptor to both σ *(CH) antibonding MO and lone pairs of CI atom.     

Anomeric effects in the symmetrical and asymmetrical structures of triethylamine. Blue-shifts of the C-h stretching vibrations in complexed and protonated triethylamine

Quantum mechanical calculations using density functional theory with the hybrid B3LYP functional and the 6-31++G(d,p) basis set are performed on isolated triethylamine (TEA), its hydrogen-bond complex with phenol, and protonated TEA. The calculations include the optimized geometries and the results of a natural bond orbital (NBO) analysis (occupation of sigma* orbitals, hyperconjugative energies, and atomic charges). The harmonic frequencies of the C-H stretching vibrations of TEA are predicted at the same level of theory. Two stable structures are found for isolated TEA. In the most stable symmetrical structure (TEA-S), the three C-C bond lengths are equal and one of the C-H bond of each of the three CH2 groups is more elongated than the three other ones. In the asymmetrical structure (TEA-AS), one of the C-C bonds and two C-H bonds of two different CH2 groups are more elongated than the other ones. These structures result from the hyperconjugation of the N lone pair to the considered sigma*(C-H) orbitals (TEA-S) or to the sigma*(C-C) and sigma*(C-H) orbitals of the CH2 groups (TEA-AS). The formation of a OH...N hydrogen bond with phenol results in a decrease of the hyperconjugation, a contraction of the C-H bonds, and blue-shifts of 28-33 cm-1 (TEA-S) or 40-48 cm-1 (TEA-AS) of the nus(CH2) vibrations. The nu(CH3) vibrations are found to shift to a lesser extent. Cancellation of the lone pair reorganization in protonated TEA-S and TEA-AS results in large blue-shifts of the nu(CH2) vibrations, between 170 and 190 cm-1. Most importantly, in contrast with the blue-shifting hydrogen bonds involving C-H groups, the blue-shifts occurring at C-H groups not participating in hydrogen bond formation is mainly due to a reduction of the hyperconjugation and the resulting decrease in the occupation of the corresponding sigma*(C-H) orbitals. A linear correlation is established between the C-H distances and the occupation of the corresponding sigma*(C-H) orbitals in the CH2 groups.     

Evidence for HOOO radicals in the formation of alkyl hydrotrioxides (ROOOH) and hydrogen trioxide (HOOOH) in the ozonation of C-H bonds in hydrocarbons.

Low-temperature ozonation of cumene (1a) in acetone, methyl acetate, and tert-butyl methyl ether at -70 degrees C produced the corresponding hydrotrioxide, C(6)H(5)C(CH(3))(2)OOOH (2a), along with hydrogen trioxide, HOOOH. Ozonation of triphenylmethane (1b), however, produced only triphenylmethyl hydrotrioxide, (C(6)H(5))(3)COOOH (2b). These observations, together with the previously reported experimental evidence, seem to support the "radical" mechanism for the first step of the ozonation of the C-H bonds in hydrocarbons, i.e., the formation of the caged radical pair (R(**)OOOH), which allows both (a) collapse of the radical pair to ROOOH and (b) the abstraction of the hydrogen atom from alkyl radical R(*) by HOOO(*) to form HOOOH. The B3LYP/6-311++G(d,p) (ZPE) calculations revealed that HOOO radicals are considerably stabilized by forming intermolecularly hydrogen-bonded complexes with acetone (BE = 8.55 kcal/mol) and dimethyl ether (7.04 kcal/mol). This type of interaction appears to be crucial for the relatively fast reactions (and the formation of the polyoxides in relatively high yields) in these solvents, as compared to the ozonations run in nonbasic solvents. However, HOOO radicals appear to be not stable enough to abstract hydrogen atoms outside the solvent cage, as indicated by the absence of HOOOH among the products in the ozonolysis of triphenylmethane. The decomposition of alkyl hydrotrioxides 2a and 2b involves a homolytic cleavage of the RO-OOH bond with subsequent "in cage" reactions of the corresponding radicals, while the decomposition of HOOOH is most likely predominantly a "pericyclic" process involving one or more molecules of water acting as a bifunctional catalyst to produce water and singlet oxygen (Delta(1)O(2)).     

Methane activation on Pt and Pt4: a density functional theory study

The activation mechanisms of a methane molecule on a Pt atom (CH4-Pt) and on a Pt tetramer (CH4-Pt4) were investigated using density functional theory (B3LYP and PW91) calculations. The results from these two functionals are different mostly in predicting the reaction barrier, in particular for the CH4-Pt system. A new lower energy pathway was identified for the CH4 dehydrogenation on a Pt atom. In the new pathway, the PtCH2 + H2 products were formed via a transition state, in which the Pt atom forms a complex with carbene and both dissociated hydrogen atoms. We report here the first theoretical study of methane activation on a Pt4 cluster. Among the five single steps toward dehydrogenation, our results show that the rate-limiting step is the third step, that is, breaking the second C-H bond, which requires overcoming an energy barrier of 28 kcal/mol. On the other hand, the cleavage of the first C-H bond, that is, the first reaction step, requires overcoming an energy barrier of 4 kcal/mol.     

Cobalt-mediated selective B-H activation and formation of a Co-B bond in the reaction of the 16-electron CpCo half-sandwich complex containing an o-carborane-1,2-dithiolate ligand with ethyl diazoacetate

The reaction of the 16-electron half-sandwich complex CpCo(S(2)C(2)B(10)H(10)) (1; Cp = cyclopentadienyl) with ethyl diazoacetate (EDA) at ambient temperature leads to compounds CpCo(S(2)C(2)B(10)H(10))(CHCO(2)Et) (2), CpCo(S(2)C(2)B(10)H(8))(CHCO(2)Et)(CH(2)CO(2)Et)[CH(CO(2)Et)(CH(2)CO(2)Et)] (3), CpCo(S(2)C(2)B(10)H(9))(CH(2)CO(2)Et)(CHCO(2)Et)(2) (4), CpCo(S(2)C(2)B(10)H(9))(CHCO(2)Et)(CH(2)CO(2)Et) (5), and CpCo(S(2)C(2)B(10)H(9))(CHCO(2)Et)(2)(CH(2)CO(2)Et) (6). In 2, the EDA molecule has been inserted into one Co-S bond in 1 with the loss of N(2) to form an 18-electron compound containing a three-membered metallacyclic ring. In 3, two B-H bonds of the carborane cage have been activated and the unusual B4-H bond activation leads to the formation of a stable Co-B bond. Two EDA molecules are inserted into the Co-B3 bond to generate an unexpected six-membered heterocyclic ring Co-B-B-C-C-O. In 4, a stable Co-B bond is present as well but in the position B3/B6, and two EDA molecules are inserted into one Co-S bond to produce a five-membered heterocyclic ring Co-C-C-C-O. In 5, one EDA is inserted into the Co-B bond with the formation of a C-B bond in the position B3/B6. One more EDA is inserted into the Co-S bond in 5 to generate 6. Upon heating, 6 loses the BH vertex close to the two carbon atoms to lead to CpCo(S(2)C(2)B(9)H(9))(CHCO(2)Et)(CH(2)CO(2)Et)(2) (7) containing a nido-C(2)B(9) unit. All of the new compounds 2-7 were characterized by NMR spectroscopy ((1)H, (11)B, and (13)C), mass spectrometry, IR spectroscopy, and elemental analysis, and their solid-state structures were further characterized by X-ray structural analysis.     

Fe原子活化乙烷的微观反应机理

本文采用密度泛函理论B3LYP方法在6-311 G(d,p)基组水平上研究了Fe原子催化乙烷反应的微观反应机理,优化了反应过程中各反应物、中间体、过渡态和产物的构型,并在同一水平上计算了反应中各驻点的振动频率,运用自然键轨道理论(NBO)方法分析了各物质的成键情况和轨道间相互作用。Fe原子对乙烷的活化过程可分为C-C键活化及C-H键活化,分别释放出CH4和H2。     

Novel reactivity mode of hydroxamic acids: a metalla-pinner reaction

The reaction between the nitrile complex trans-[PtCl(4)(EtCN)(2)] and benzohydroxamic acids RC(6)H(4)C([double bond]O)NHOH (R = p-MeO, p-Me, H, p-Cl, o-HO) proceeds smoothly in CH(2)Cl(2) at approximately 45 degrees C for 2-3 h (sealed tube) or under focused 300 W microwave irradiation for approximately 15 min at 50 degrees C giving, after workup, good yields of the imino complexes [PtCl(4)[NH[double bond]C(Et)ON[double bond]C(OH)(C(6)H(4)R)](2)] which derived from a novel metalla-Pinner reaction. The complexes [PtCl(4)[NH[double bond]C(Et)ON[double bond]C(OH)(C(6)H(4)R)](2)] were characterized by elemental analyses (C, H, N), FAB mass spectrometry, and IR and (1)H and (13)C[(1)H] spectroscopies, and [PtCl(4)[NH[double bond]C(Et)ON[double bond]C(OH)(Ph)](2)] (as the bis-dimethyl sulfoxide solvate), by X-ray single-crystal diffraction. The latter disclosed its overall trans-configuration with the iminoacyl species in the hydroximic tautomeric form in E-configuration which is held by N[bond]H...N hydrogen bond between the imine [double bond]NH atom and the hydroximic N atom.     

利用结构相关性方法研究碳氢键活化反应C-H+M■的机理

本文利用结构相关(?)方法对碳氢键活化反应的氧化加成反应机理进行了研究.建立了反应的过渡态,并对反应途径进行了描述.根据所得到的反应途径对碳氢键活化研究中的一些问题进行了解释.     

利用结构相关性方法研究碳氢键活化反应C-H+M⇔C-M-H的机理

本文利用结构相关性方法对碳氢键活化反应的氧化加成反应机理进行了研究.建立了反应的过渡态,并对反应途径进行了描述.根据所得到的反应途径对碳氢键活化研究中的一些问题进行了解释.     

醋酸乙烯酯基桥连铁硫配合物(σ,π-μ-CH3CO2C=CH2)(μ-RS)Fe2CO)6的制备及结构鉴定

本文报道乙酰氯同[μ-CO)(μ-RS)Fe2(CO]Et3NH相作用生成了标题化合物, 除用碳氢分析, IR, 'HNMR及X衍射技术表征这类配合物的结构和构象外, 还对形成此类产物的过程进行了初步讨论。     

Methane activation by titanium monoxide molecules: a matrix isolation infrared spectroscopic and theoretical study

Reactions of titanium monoxides with methane have been investigated using matrix isolation infrared spectroscopy and theoretical calculations. Titanium derivatives of several simple oxyhydrocarbons have been prepared and identified. The titanium monoxide molecules prepared by laser evaporation of bulk TiO2 target reacted with methane to form the TiO(CH4) complex in solid argon, which was predicted to have C3v symmetry with the oxygen atom coordinated to one hydrogen atom of the methane molecule. The complex rearranged to the CH3Ti(O)H titano-acetaldehyde molecule upon visible (lambda > 500 nm) irradiation. The titano-acetaldehyde molecule sustained further photochemical rearrangement to the CH2Ti(H)OH titano-vinyl alcohol molecule, which was characterized to be a simple carbene complex involving agostic bonding. The CH2Ti(H)OH molecule reacted with a second methane to form the (CH3)2Ti(H)OH titano-isopropyl alcohol molecule spontaneously on annealing. The (CH3)2Ti(H)OH molecule also can be produced via UV photon-induced rearrangement of the CH3Ti(O)H(CH4) complex.