N-Aryloxide-Amidinate Thorium Complexes.

An N-aryloxide-amidine ligand (1), [ONNO] ligand, integrating phenoxide (PhO-) and amidine ligands through methylene linkers, was employed in actinide chemistry. Upon reaction of the deprotonated ligand with ThCl4(DME)2 in ether, the corresponding dimer complex 2 was obtained. Upon treatment of 2 with KCp* (Cp* = Cp(Me)5) in tetrahydrofuran, the corresponding {[ONNO]ThIVCp*(LiCl)}2 (4) was obtained. In complex 2, the two ArO- arms bonded from the same ligand to different ThIV centers. In contrast, both ArO- arms coordinated to the same metal center in 4. Notably, when a mixture of 2 and bipyridine was treated with one or two equiv of KC8, the [ONNO]ThIV-bipyridyl•̅ radical dimer complex (5) and [ONNO]ThIV-bipyridyl2- dianionic dimer species (6) were obtained, respectively.

Unusual Electronic Structures of an Electron Transfer Series of [Cr(µ-η1 : η1 -N2 )Cr]0/1+/2.

In dinitrogen (N2 ) fixation chemistry, bimetallic end-on bridging N2 complexes M(µ-η1 : η1 -N2 )M can split N2 into terminal nitrides and hence attract great attention. To date, only 4d and 5d transition complexes, but none of 3d counterparts, could realize such a transformation. Likewise, complexes {[Cp*Cr(dmpe)]2 (µ-N2 )}0/1+/2+ (1-3) are incapable to cleave N2 , in contrast to their Mo congeners. Remarkably, cross this series the N-N bond length of the N2 ligand and the N-N stretching frequency exhibit unprecedented nonmonotonic variations, and complexes 1 and 2 in both solid and solution states display rare thermally activated ligand-mediated two-center spin transitions, distinct from discrete dinuclear spin crossovers. In-depth analyses using wave function based ab initio calculations reveal that the Cr-N2 -Cr bonding in complexes 1-3 is distinguished by strong multireference character and cannot be described by solely one electron configuration or Lewis structure, and that all intriguing spectroscopic observations originate in their sophisticate multireference electronic structures. More critical is that such multireference bonding of complexes 1-3 is at least a key factor that contributes to their kinetic inertness toward N2 splitting. The mechanistic understanding is then used to rationalize the disparate reactivity of related 3d M(µ-η1 : η1 -N2 )M complexes compared to their 4d and 5d analogs.

Dinitrogen Activation and Functionalization Affording Chromium Diazenido and Hydrazido Complexes.

ConspectusThe activation and functionalization of N2 to form nitrogen-element bonds have long posed challenges to industrial, biological, and synthetic chemists. The first transition-metal dinitrogen complex prepared by Allen and Senoff in 1965 provoked researchers to explore homogeneous N2 fixation. Despite intensive research in the last six decades, efficient and quantitative conversion of N2 to diazenido and hydrazido species remains problematic. Relative to a plethora of reactions to generate N2 complexes, their functionalization reactions are rather rare, and the yields are often unsatisfactory, emphasizing the need for systematic investigations of the reaction mechanisms.In this Account, we summarize our recent work on the synthesis, spectroscopic features, electronic structures, and reactivities of several Cr-N2 complexes. Initially, a series of dinuclear and trinuclear Cr(I)-N2 complexes bearing cyclopentadienyl-phosphine ligands were accessed. However, they cannot achieve N2 functionalization but undergo oxidative addition reactions with phenylsilane, azobenzene, and other unsaturated organic compounds at the low-valent Cr(I) centers rather than at the N2 unit. Further reduction of these Cr(I) complexes leads to the formation of more activated mononuclear Cr(0) bis-dinitrogen complexes. Remarkably, silylation of the cyclopentadienyl-phosphine Cr(0)-N2 complex with Me3SiCl afforded the first Cr hydrazido complex. This process follows the distal pathway to functionalize the Nß atom twice, yielding an end-on η1-hydrazido complex, Cr(III)═N-N(SiMe3)2. In contrast, upon substitution of the phosphine ligand in the Cr(0)-N2 complex with a N-heterocyclic carbene (NHC) ligand, the corresponding reaction with Me3SiCl proceeds via the alternating pathway; the silylation occurs at both Nα and Nß atoms and generates a side-on η2-hydrazido complex, Cr(III)(η2-Me3SiN-NSiMe3). Both silylation reactions are inevitably accompanied by the formation of Cr(III) hydrazido complexes and Cr(II) chlorides with a 2:1 ratio. These processes exhibit a peculiar '3-4-2-1' stoichiometry (i.e., treating 3 equiv of Cr(0)-N2 complexes with 4 equiv of Me3SiCl yields 2 equiv of Cr(III) disilyl-hydrazido complexes and 1 equiv of Cr(II) chloride). Upon replacing the monodentate phosphine and/or NHC ligand with a bisphosphine ligand, a monodinitrogen Cr(0) complex, instead of the bis-dinitrogen Cr(0) complexes, is obtained; consequently, the silylation reactions progress via the normal two-electron route, which passes through Cr(II)-N═N-R diazenido species as an intermediate and furnishes [Cr(IV)═N-NR2]+ hydrazido as the final products. More importantly, this type of Cr(0)-N2 complex can be not only silylated but also protonated and alkylated proficiently. All of the second-order reaction rates of the first and second transformations are determined along with the lifetimes of the intervening diazenido species. Based on these findings, we have successfully carried out nearly quantitative preparations of the Cr(IV) hydrazido species with unmixed or hybrid substituents.The studies of Cr-N2 systems provide effective approaches for the activation and functionalization of N2, deepening the understanding of N2 electrophilic attack. We hope that this Account will inspire more discoveries related to the transformation of gaseous N2 to high-value-added nitrogen-containing organic compounds.

Syntheses and Characterizations of Hetero-Bimetallic Chromium-Dinitrogen Transition-Metal Complexes.

In the domain of N2 activation, hetero-bimetallic dinitrogen complexes are garnering substantial interest due to their potential to induce polarization in nonpolar N2 gas. Herein, we present the syntheses and characterizations of three novel hetero-multimetallic dinitrogen complexes: Cp*Cr(depe)N2V(depe)Me[O, P, O] 5, Cp*Cr(depe)N2V(depe)Tipp[O, P, O] 6, and [Cp*Cr(depe)N2]2TiTipp[O, P, O] 7. These complexes were synthesized via a transmetalation process involving the treatment of [Cr0-N2]- complex 4 with vanadium and titanium chloride complexes bearing alkyl or aryl substituted bis(o-hydroxyphenyl)-phenyl phosphine R[O, P, O] ligand (alkyl = methyl, aryl = 2,4,6-tri-isopropylbenzene). X-ray analysis shows that complexes 5 and 6 exhibit heterodinuclear structures, while complex 7 exhibits a heterotrinuclear core with two N2 ligands concurrently coordinated to two chromium and one titanium atoms. Raman spectroscopic data show that the N-N stretching vibration of the N2 moiety is clearly downshifted relative to free N2 and to mononuclear [Cr0-N2]- complex 4.

N-aryloxide-amidinate group 4 metal complexes.

A N-aryloxide-amidine ligand (H3L), integrating phenoxide (PhO-) and amidine ligands through methylene linkers, has been synthesized from 2-(aminomethyl)-6-(tert-butyl)phenol in two steps. Upon reacting the deprotonated H3L ligand with group 4 metal chloride MIVCl4, a corresponding (LMIV-Cl)2 dimer could be obtained. The coordination modes exhibit variation depending on the radius of the metal ions. In the case of (LTiIV-Cl)2, the two ArO- arms from the same ligand bond to two different Ti(IV) centers, while in the case of (LZrIV/HfIV-Cl)2, both ArO- arms coordinate with the same metal center. Moreover, the two C-N bonds in the amidinate moiety are localized in (LTiIV-Cl)2, whereas they delocalize in (LZrIV-Cl)2. Notably, (LHfIV-Cl)2 could further react with one equivalent of HfCl4, yielding the binuclear metal azide in the presence of KN3 and LiCl, where the coordination mode of the amidinate moiety changed from the bidentate chelating type to the bimetallic bridging coordination.

Snapshots of Early-Stage Quantitative N2 Electrophilic Functionalization.

Electrophilic functionalization of N2 moieties in metal dinitrogen complexes typically initiates the catalytic synthesis of N-containing molecules directly from N2. Despite intensive research in the last six decades, how to efficiently and even quantitatively convert N2 into diazenido and hydrazido species still poses a great challenge. In this regard, systematic and comprehensive investigations to elucidate the reaction intricacies are of profound significance. Herein, we report a kinetic dissection on the first and second electrophilic functionalization steps of a new Cr0-N2 system with HOTf, MeOTf, and Me3SiOTf. All reactions pass through fleeting diazenido intermediates and furnish long-lived final hydrazido products, and both steps are quantitative conversions at low temperatures. All of the second-order reaction rates of the first and second transformations were determined as well as the lifetimes of the intervening diazenido species. Based on these findings, we succeeded in large-scale and near-quantitative preparation of all hydrazido species.

From Dinitrogen to N-Containing Organic Compounds: Using Li2 CN2 as a Synthon.

Through the synergies of a heterogeneous synthetic approach and a homogeneous synthetic methodology, N-containing organic compounds can be synthesized via activated N-containing species prepared from N2 gas and suitable carbon sources. From N2 , carbon, and LiH, we have previously succeeded in the high-yield preparation of Li2 CN2 as the activated N-containing species. In this work, we applied Li2 CN2 as a novel synthetic synthon for constructing N-containing organic compounds. A series of reaction models, including a substitution reaction, cycloaddition reaction, and transition metal-catalyzed coupling reaction, were successfully performed using Li2 CN2 under mild conditions. Various valuable cyanamides, carbodiimides, N-aryl cyanamides and 1,2,4-triazole derivatives were readily synthesized in moderate to excellent yields. With this method, the 15 N-labeled products, including oxazolidine derivatives with anti-cancer activity, could also be facilely prepared from 15 N2 gas.

Dinitrogen Functionalization Affording Chromium Diazenido and Side-on η2-Hydrazido Complexes.

Isolation of key intermediate complexes in dinitrogen functionalization is crucial for elucidating the mechanistic details and further investigation. Herein, the synthesis and characterization of (µ-η1:η1-N2)(η1-N2)-Cr(I) 3 and (η1-N2)2-Cr(0) complexes 4 supported by Cp* (Cp* = C5Me5) and NHC ligands were reported. Further functionalization of Cr(0)-N2 complex 4 with silyl halides delivered the key intermediates in the alternating pathway, the chromium diazenido complex 5 and the chromium side-on η2-hydrazido complex 6. Protonation of 6 led to the quantitative formation of N2H4. Moreover, the [η2-Me3SiNNSiMe3]2- unit in 6 enabled N-C bond formation reactions with CO2 and tBuNCO, giving the corresponding N,O-chelating hydrazidochromium complexes 7 and 8, respectively.

Dinitrogen activation by a phosphido-bridged binuclear cobalt complex.

By reacting the semi-rigid PNP ligand with CoBr2, the corresponding complex PNPCoBr (1) was obtained. The reduction of 1 with excess amounts of KC8 in THF under a N2 atmosphere yielded a binuclear cobalt dinitrogen anion complex [Co(µ-Cy2P)PCyN2]2K (2) via the C-P bond cleavage of the PNP ligand. By adding 2,2,2-cryptand into complex 2, an ion pair Co complex, [Co(µ-Cy2P)PCyN2]2K(crypt-222) (3), could be effectively prepared. The structures of 1, 2, and 3 have been determined by single-crystal X-ray diffraction analysis, and N2 is moderately activated in complexes 2 and 3. There is a Co-Co bond in 2 and 3 suggested by DFT calculations. Compounds 1 and 2 display catalytic activity for the transformation of N2 into N(SiMe3)3.

Cobalt Cyclopentadienyl-Phosphine Dinitrogen Complexes.

By applying the potassium salts of cyclopentadienyl-phosphine ligands LK to CoCl2 , the corresponding cobalt chlorides (1, LCoII Cl) were prepared. By reducing complexes 1 with KHBEt3 under a N2 atmosphere, bridging end-on complexes, LCoI -N2 -CoI L (2 a and 2 b), were successfully obtained. 15 N2 -labeled [15 N2 ]-2 a was prepared under 15 N2 /14 N2 exchange in THF solution. LCoI -N2 -CoI L complex 2 a could react with P4 molecules to release N2 and generate a Co-P4 -Co moiety 4. Further reduction of complex 2 b led to cleavage of a P-C bond in the cyclopentadienyl-phosphine ligand to provide novel µ-PCy2 -bridged Co0 -N2 complex 5. DFT calculations confirmed the experimental observations.

Synthesis and isolation of dinuclear N,C-chelate organoboron compounds bridged by neutral, anionic, and dianionic 4,4'-bipyridine via reductive coupling of pyridines.

The reaction of Bppy(Mes)2 (BN1; ppy = 2-phenylpyridine) and BCH2ppy(Mes)2 (BN3) with the reducing reagent KC8 resulted in C-C bond formation via intermolecular radical coupling to generate the 4,4'-bipyridyl ligand compounds BN2 and BN4. Adding 1 equivalent of KC8 to a THF solution of BN2 and BN4 generated the 4,4'-bipyridyl radical anions BN2K and BN4K. The dianion species BN2K2 and BN4K2 could be obtained by adding 2 equivalents of KC8 to the THF solution of BN2 and BN4. In the presence of 2,2,2-cryptand or 18-crown-6, the radical anion salt BN2K(crypt) and the dianion salt BN2K2(18c6)2 were isolated for single-crystal X-ray diffraction analysis. Structural, spectroscopic, and computational studies were performed on the three species of BN2 derivatives (neutral, radical anion, and dianion species). BN2 and BN4 were stable and did not undergo photoisomerization or photoelimination under UV light irradiation.

(n-Bu)4NBr-Promoted N2 Splitting to Molybdenum Nitride.

Splitting of N2 via six-electron reduction and further functionalization to value-added products is one of the most important and challenging chemical transformations in N2 fixation. However, most N2 splitting approaches rely on strong chemical or electrochemical reduction to generate highly reactive metal species to bind and activate N2, which is often incompatible with functionalizing agents. Catalytic and sustainable N2 splitting to produce metal nitrides under mild conditions may create efficient and straightforward methods for N-containing organic compounds. Herein, we present that a readily available and nonredox (n-Bu)4NBr can promote N2-splitting with a Mo(III) platform. Both experimental and theoretical mechanistic studies suggest that simple X- (X = Br, Cl, etc.) anions could induce the disproportionation of MoIII[N(TMS)Ar]3 at the early stage of the catalysis to generate a catalytically active {MoII[N(TMS)Ar]3}- species. The quintet MoII species prove to be more favorable for N2 fixation kinetically and thermodynamically, compared with the quartet MoIII counterpart. Especially, computational studies reveal a distinct heterovalent {MoII-N2-MoIII} dimeric intermediate for the N≡N triple bond cleavage.

Trisyl-based multidentate ligands: synthesis and their transition-metal complexes.

Herein we report the synthesis and applications of unusual trisyl-based multidentate ligands [trisyl = tris(trimethylsilyl)methyl, -C(SiMe3)3]. First, by applying a new trisyl synthon (Me3Si)2CH(SiMe2CH2Cl) 1, trisyl-based S- or N-containing compounds 2 were efficiently obtained. On treatment of these compounds 2 with MeLi, their corresponding S- or N-coordinated pincer-like trisyl-based lithium salts 3, including the S-bridged ditrisyl compound 3a [Li{C(SiMe3)2SiMe2CH2SCH2SiMe2C(SiMe3)2}Li(DME)3] and the N-coordinated monotrisyl compounds 3b [(NacNacDippLiCH2SiMe2C(SiMe3)2Li(THF)], 3c [Li(THF){C(SiMe3)2SiMe2CH2N(Me)CH2C5H4N-2}], and 3d [Li{C(SiMe3)2SiMe2CH2N(Me)CH2CH2N(iPr)2}] were synthesized and structurally characterized by single-crystal X-ray structural analysis. Second, to test these novel lithium salts as straightforward precursors for the synthesis of transition-metal complexes with unique structures, these lithium salts were applied to react with MCl2 (M = Cr, Mn, Fe, Co). Their corresponding transition-metal complexes 4-8 were obtained in high yields and structurally characterized by single-crystal X-ray structural analysis. Third, the preliminary reactivities of compound 4 were explored.

Synthesis of pyrimidines from dinitrogen and carbon.

The element nitrogen and nitrogenous compounds are vital to life. The synthesis of nitrogen-containing compounds using dinitrogen as the nitrogen source, not through ammonia, is of great interest and great value but remains a grand challenge. Herein, we describe a strategy to realize this transformation by combining the heterogeneous approach with the homogeneous methodology. The N2 molecule was first fixed with carbon and LiH through a one-pot heterogeneous process, forming Li2CN2 as an 'activated' nitrogen source with high efficiency. Then subsequent homogeneous treatments of Li2CN2 to construct the organic synthon carbodiimide and the RNA/DNA building block pyrimidines were fulfilled. By using 15N2 as the feedstock, their corresponding 15N-labeled carbodiimide and pyrimidines were readily obtained. This homogeneous-heterogeneous synergy strategy will open a new chapter for N2 transformation.

Direct conversion of N2 and O2: status, challenge and perspective.

As key components of air, nitrogen (N2) and oxygen (O2) are the vital constituents of lives. Synthesis of NO2, and C-N-O organics direct from N2 and O2, rather than from an intermediate NH3 (known as the Haber-Bosch process), is tantalizing. However, the extremely strong N≡N triple bond (945 kJ mol-1) and the nonpolar stable electron configuration of dinitrogen lead to its conversion being extensively energy demanding. The further selective synthesis of high-value C-N-O organics directly from N2, O2 and C-containing molecules is attractive yet greatly challenging from both scientific and engineering perspectives. Enormous efforts have been dedicated to the direct conversion of N2 and O2 via traditional and novel techniques, including thermochemical, plasma, electrochemical, ultrasonic and photochemical conversion. In this review, we aim to provide a thorough comprehension of the status and challenge of the direct conversion of N2, O2 and C-containing molecules (particularly N2 and O2). Moreover, we will propose some future perspectives to stimulate more inspiration from the scientific community to tackle the scientific and engineering challenges.

C,C- and C,N-Chelated Organocopper Compounds.

Copper-catalyzed and organocopper-involved reactions are of great significance in organic synthesis. To have a deep understanding of the reaction mechanisms, the structural characterizations of organocopper intermediates become indispensable. Meanwhile, the structure-function relationship of organocopper compounds could advance the rational design and development of new Cu-based reactions and organocopper reagents. Compared to the mono-carbonic ligand, the C,N- and C,C-bidentate ligands better stabilize unstable organocopper compounds. Bidentate ligands can chelate to the same copper atom via η2-mode, forming a mono-cupra-cyclic compounds with at least one acute C-Cu-C angle. When the bidentate ligands bind to two copper atoms via η1-mode at each coordinating site, the bimetallic macrocyclic compounds will form nearly linear C-Cu-C angles. The anionic coordinating sites of the bidentate ligand can also bridge two metals via µ2-mode, forming organocopper aggregates with Cu-Cu interactions and organocuprates with contact ion pair structures. The reaction chemistry of some selected organocopper compounds is highlighted, showing their unique structure-reactivity relationships.

Metalla-aromatics: Planar, Nonplanar, and Spiro.

ConspectusThe concept of aromaticity is one of the most fundamental principles in chemistry. It is generally accepted that planarity is a prerequisite for aromaticity, and typically the more planar the geometry of an aromatic compound is, the stronger aromatic it is. However, it is not always the case, particularly when transition metals are involved in conjugation and electron delocalization of aromatic systems, i.e., metalla-aromatics. Because of the intrinsic nature of transition-metal orbitals, besides planar geometries, the most stable molecular structures of metalla-aromatic compounds could take nonplanar and even spiro geometries. In this Account, we outline several unprecedented types of metalla-aromatics developed recently in our research group.Around seven years ago, we found that 1,4-dilithio-1,3-butadienes, dilithio reagents with π-conjugation, could function as non-innocent ligands and react with low-valent transition-metal complexes, generating monocyclic metalla-aromatic compounds. Later on, by taking advantage of the unique behavior of dilithio reagents and the intrinsic nature of different transition metals, we have synthesized a series of metalla-aromatic compounds, of which four types are discussed here, and each of them represents the first of its kind. First, nearly planar aromatic dicupra[10]annulenes, a 10 π-electron aromatic system with two bridging Cu atoms participating in the orbital conjugation and electron delocalization, are synthesized by annulating two dilithio reagents with two Cu(I) complexes.Second, four kinds of spiro metalla-aromatics, featuring planar (with Pd, Pt, or Rh as the spiro atom) geometry with a whole 10π aromatic system, octahedral (tris-spiro metalla-aromatics with V as the spiro atom) geometry with an entire 40π Craig-Möbius aromatic system, tetrahedral (with Mn as the spiro atom) geometry having two independent and perpendicular 6π planar aromatic rings, and tetrahedral (with Mn as the spiro atom) geometry with one planar and one nonplanar 6π aromatic rings, respectively, are generated. In sharp contrast to spiroaromaticity with carbon acting as the spiro atom described in Organic Chemistry, the metal spiro atom herein takes part in orbital conjugation and electron delocalization.Third, nonplanar aromatic butadienyl diiron complexes are realized. Different from planar aromatic systems featuring delocalized π-type overlap, this nonplanar metalla-aromaticity is achieved by the novel σ-type overlap between the two Fe 3dxz orbitals and the butadienyl π orbital, forming a 6π aromatic system. Fourth, dinickelaferrocene, a ferrocene analogue with two aromatic nickeloles, is synthesized from our monocyclic aromatic dilithionickelole and FeBr2. The aromaticity of dinickelaferrocene and its nickelole ligands is realized by electron back-donation from the Fe 3d orbital to the π* orbital of nickeloles, which also deepens our understanding of the origin of aromaticity.The search for unprecedented and exciting aromatic systems, particularly with transition metals being involved, will continue to drive this intriguing research field forward. Given the synthetic strategies and various types of metalla-aromatics developed and described, diversified metalla-aromatics of interesting structures and reaction chemistry, novel chemical bonding modes, and useful functions can be expected.

A tris-spiro metalla-aromatic system featuring Craig-Möbius aromaticity.

As aromaticity is one of the most fundamental concepts in chemistry, the construction of aromatic systems has long been an important subject. Herein, we report the synthesis and characterization of a tris-spiroaromatic complex, hexalithio spiro vanadacycle 2. The delocalization of the four electrons within the two V 3d orbitals and the π* orbitals of the three biphenyl ligands leads to a 40π Craig-Möbius aromatic system with three metalla-aromatic rings, as revealed by both experimental measurements and theoretical analyses. For comparison, if Cr is used instead of V, a similar Craig-Möbius aromatic system can not be generated. In this case, pentalithio spiro chromacycle 3 is obtained, and the Cr center uses its two 3d orbitals to form two independent metalla-aromatic rings. This work presents a type of aromatic systems that will contribute to both aromaticity theory and organometallic chemistry.

Synthesis, Structure, and Magnetic Properties of Rare-Earth Bis(diazabutadiene) Diradical Complexes.

New kinds of diradical rare-earth metal complexes supported by diazabutadiene (DAD) ligands, [(DAD)2LnN(TMS)2] (1; Ln = Dy, Lu; TMS = SiMe3), were synthesized and studied. They showed a new [radical-Ln-radical] alignment with distorted square-pyramidal geometry. Structural and density functional theory analysis illustrated the radical anionic nature of the ligands. Magnetic studies revealed antiferromagnetic coupling of the two radicals in 1-Lu. 1-Dy showed typical single-molecule-magnet (SMM) behavior with an effective energy barrier of 231 K, which is much higher than those of similar radical-containing SMMs. Magnetostructural analysis suggests that the anionic [N(TMS)2]- group plays a vital role in the SMM property. This study provides a new platform for further improving the performance of radical-Ln SMMs.

Cyclic Bis-alkylidene Complexes of Titanium and Zirconium: Synthesis, Characterization, and Reaction.

Transition-metal alkylidenes have exhibited wide applications in organometallic chemistry and synthetic organic chemistry, however, cyclic Schrock-carbene-like bis-alkylidenes of group 4 metals with a four-electron donor from an alkylidene have not been reported. Herein, the synthesis and characterization of five-membered cyclic bis-alkylidenes of titanium (4 a,b) and zirconium (5 a,b) are reported, as the first well-defined group 4 metallacyclopentatrienes, by two-electron reduction of their corresponding titana- and zirconacyclopentadienes. DFT analyses of 4 a show a four-electron donor (σ-donation and π-donation) from an alkylidene carbon to the metal center. The reaction of 4 a with N,N'-diisopropylcarbodiimide (DIC) leads to the [2+2]-cycloaddition product 6. Compound 4 a reacted with CO, affording the oxycyclopentadienyl titanium complex 7. These reactivities demonstrate the multiple metal-carbon bond character. The reactions of 4 a or 5 a with cyclooctatetraene (COT) or azobenzene afforded sandwich titanium complex 8 or diphenylhydrazine-coordinated zirconacyclopentadiene 9, respectively, which exhibit two-electron reductive ability.