Search

Azidation of alkenes is an efficient protocol to synthesize organic azides which are important structural motifs in organic synthesis. Enantioselective radical azidation, as a useful strategy to install a C-N3 bond, remains challenging due to the inherently instability and unique structure of radicals. Here, we disclose an efficient enantioselective radical carboazidation and diazidation of α,β-unsaturated ketones and amides catalyzed by chiral N,N'-dioxide/Fe(OTf)2 complexes. An array of substituted alkenes was transformed to the corresponding α-azido carbonyl derivatives in good to excellent enantioselectivities, benefiting the preparation of chiral α-amino ketones, vicinal amino alcohols, and vicinal diamines. Control experiments and mechanistic studies proved the radical pathway in the reaction process. The DFT calculations showed that the azido transferred to the radical intermediate via an intramolecular five-membered transition state with the internal nitrogen of the Fe-N3 species.

Vinylcarbene insertion into the nitrogen-hydrogen (N-H) bond of amines allows direct access to α,β-unsaturated γ-amino acid derivatives, meeting a marked challenge in the control of regio- and enantioselectivities. Here, we report a highly γ-selective and enantioselective insertion into N-H bonds of aliphatic or aromatic secondary amines with vinyl substituted α-diazo pyrazoleamides using a high-spin chiral N,N'-dioxide/cobalt(II) complex catalyst. The method affords a wide variety of valuable optically active Z- and E-type vinyl γ-amino amides. Calculation reveals a spin state change from the quartet cobalt(II) complex to a doublet Co(II)-carbene species for facile Z-selective and enantioselective nucleophilic addition.

The homologation of ketones with diazo compounds is a useful strategy to synthesize one-carbon chain-extended acyclic ketones or ring-expanded cyclic ketones. However, the asymmetric homologation of acyclic ketones with α-diazo esters remains a challenge due to the lower reactivity and complicated selectivity. Herein, we report the enantioselective catalytic homologation of acetophenone and related derivatives with α-alkyl α-diazo esters utilizing a chiral scandium(III) N,N'-dioxide as the Lewis acid catalyst. This reaction supplies a highly chemo-, regio-, and enantioselective pathway for the synthesis of optically active β-keto esters with an all-carbon quaternary center through highly selective alkyl-group migration of the ketones. Moreover, the ring expansion of cyclic ketones was accomplished under slightly modified conditions, affording a series of enantioenriched cyclic β-keto esters. Density functional theory calculations have been carried out to elucidate the reaction pathway and possible working models that can explain the observed regio- and enantioselectivity.

Nickel-catalyzed intermolecular Heck reaction of cycloalkenes proceeds well with aryl triflates, mesylates and tosylates in excellent enantiomeric ratios. The asymmetric reductive Heck reaction also works with a 2-cyclopentenone ketal, which is equivalent to conjugate arylation of the enone itself. Economic Development Board (EDB) Accepted version We acknowledge financial supports from Peking University Shenzhen Graduate School, Shenzhen Bay Laboratory Insti- tute of Chemical Biology, Nanyang Technological University, GlaxoSmithKline and the Singapore Economic Development Board Trust Fund (2017 GSK-EDB Green and Sustainable Manufacturing Award) and A*STAR Science and Engineer- ing Research Council (A1783c0010).

Conformationally restricted azabicycles are becoming increasingly important in medicinal research. Asymmetric Heck bicyclization of enynes proceeds to give medicinally useful aza[3.1.0] and aza[4.1.0] bicycles with excellent enantioselectivity. The key organopalladium species after bicyclization can be trapped by silanes and terminal alkynes. Agency for Science, Technology and Research (A*STAR) Economic Development Board (EDB) Accepted version We acknowledge financial support from Peking UniversityShenzhen Graduate School, Shenzhen Bay Laboratory(21230011-Scripps), National Natural Science Foundation ofChina (NSFC 21933004), Nanyang Technological University,GSK-EDB Trust Fund (2017 GSK-EDB Green and Sustain-able Manufacturing Award) and A*STAR Science andEngineering Research Council (AME IRG A1783c0010).MP contributed DFT calculations.

The Rh-catalyzed reactions of

Herein, we report the first example of enantioselective (2+1) cycloaddition of thioketones with α-diazo pyrazoleamides for the direct synthesis of tetrasubstituted thiiranes. In the presence of chiral N,N'-dioxide/cobalt(ΙΙ) complexes (2-5 mol%), excellent efficiency (up to 99 % yield within 15 mins) and high stereoselectivity (up to19 : 1 dr and 97 % ee) are available. Elaborations of thiiranes via desulfuration have also been conducted to deliver tetrasubstituted olefins. Density functional theory calculations reveal that the reaction initiates from a doublet state cobalt(ΙΙ) carbenoid, which is followed by a quartet cobalt(ΙΙ)-bound thiocarbonyl ylide pathway. This work provides a route for the selective construction of tetrasubstituted thiiranes and olefins that are otherwise difficult to access.

A nickel complex of isoquinox promoted enantioselective conjugate arylation and heteroarylation of enones using aryl and heteroaryl halides directly. The reaction was successfully applied to stereoselective syntheses of ar-turmerone, chiral fragments of (+)-tolterodine and AZD5672. Mechanistically, experiments and calculations supported that an arylnickel(I) complex inserted to enones via an elementary 1,4-addition. National Research Foundation (NRF) We acknowledge financial support from Peking University Shenzhen Graduate School, State Key Laboratory of Chemical Oncogenomics, Guangdong Provincial Key Laboratory of Chemical Genomics, Shenzhen Bay Laboratory and Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs for J.S.Z., the National Natural Science Foundation of China (NSFC 21933004) for Y.D.W., and Singapore National Research Foundation (NRF-CRP22-2019-0002) for Y.R.C.

The enantioselective construction of quaternary carbon centers is a marked challenge in asymmetric catalysis research. It is extremely difficult when a chiral catalyst can not distinguish the facial selectivity of the substrate through bond interactions. Here we realized an enantioselective Michael reaction of silyl ketene imines to 1-acrylpyrazoles using a chiral N,N'-dioxide-Co(II) complex. The protocol is highly efficient for the construction of nitrile-, aryl-, and dialkyl-bearing carbon centers and has been successful applied in the divergent synthesis of pharmaceuticals and natural products. The through-space dispersion interactions between unbound silyl ketene imines and the 1-acrylpyrazole-bonded catalyst play a key role in facilitating the reactivity and the enantioselectivity of this process.

We herein disclose the use of tetramethylammonium fluoride (TMAF) as a direct and selective methylating agent of a variety of amides, indoles, pyrroles, imidazoles, alcohols, and thiols. The method is characterized by operational simplicity, wide scope, and ease of purification. Our computational studies suggest a concerted methylation–deprotonation as the preferred reaction pathway.

Angewandte Chemie / International edition International edition 58(33), 11395 - 11399 (2019). doi:10.1002/anie.201906063, Published by Wiley-VCH, Weinheim

Palladium catalyzes a domino Heck arylation and alkylation of nonconjugated cyclodienes to produce trans isomers of disubstituted cyclohexenes in exceptionally high enantiomeric ratios, reaching 100:1 to 200:1 in many cases. Importantly, the interactions of the two CF bonds of Josiphos and the sodium ion of malonates facilitates stereoselective allylic attack through DFT calculations and experiments. This is a new type of attractive noncovalent interactions found in organometallic catalysis. Economic Development Board (EDB) Nanyang Technological University We acknowledge financial support from Peking University Shenzhen Graduate School and Shenzhen Bay Laboratory for J.S.Z.; the National Natural Science Foundation of China (NSFC 21933004) for Y.-D.W.; Nanyang Technological University and GlaxoSmithKline and the Singapore Economic Development Board Trust Fund (2017 GSK-EDB Green & Sustainable Manufacturing Award) for Y.R.C.

Activation of C–H bonds assisted by a directing group is indispensable in organic synthesis. Among them, utilizing oxidative directing groups that can serve as an internal oxidant to drive the Mn/M...

While thiophosgene finds widespread usage on a multi-ton scale, its fluorinated counterpart S=CF2 is essentially unexplored in synthesis. Using experimental reactivity tests, ReactIR and computational techniques, we herein showcase that the solid (Me4 N)SCF3 functions as a safe reservoir for S=CF2 . A key feature is that the reactive electrophile is not simply released over time, but instead is liberated under activation with a protic nucleophile. The reactivity of S=CF2 is mild, allowing large-scale and late-stage synthetic applications without special reaction control. The mechanism was fully elucidated, including a rationalization of the role of the Me4 N cation and the origins of selectivity.

We herein disclose the use of tetramethylammonium fluoride (TMAF) as a direct and selective methylating agent of a variety of amides, indoles, pyrroles, imidazoles, alcohols, and thiols. The method is characterized by operational simplicity, wide scope, and ease of purification. Our computational studies suggest a concerted methylation-deprotonation as the preferred reaction pathway.

Fluorescent theranostics probes at the second near-IR region (NIR-II; 1.0–1.7 µm) are in high demand for precise theranostics that minimize autofluorescence, reduce photon scattering, and improve the penetration depth. Herein, we designed and synthesized an NIR-II theranostic nanoprobe 1 that incorporates a Pt(II) metallacycle 2 and an organic molecular dye 3 into DSPE-mPEG5000 (1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)-5000]). This design endows 1 with good photostability and passive targeting ability. Our studies show that 1 accurately diagnoses cancer with high resolution and selectively delivers the Pt(II) metallacycle to tumor regions via an enhanced permeability and retention effect. In vivo studies reveal that 1 efficiently inhibits the growth of tumor with minimal side effects. At the same time, improved fluorescent imaging quality and signal-to-noise ratios are shown due to the long emission wavelengths. These studies demonstrate that 1 is a potential theranostic platform for tumor diagnosis and treatment in the NIR-II region.

The role solvent plays in reactions involving frustrated Lewis pairs (FLPs)-for example, the stoichiometric mixture of a bulky Lewis acid and a bulky Lewis base-still remains largely unexplored at the molecular level. For a reaction of the phosphorus/boron FLP and dissolved CO2 gas, first principles (Born-Oppenheimer) molecular dynamics with explicit solvent reveals a hitherto unknown two-step reaction pathway-one that complements the concerted (one-step) mechanism known from the minimum-energy-path calculations. The rationalization of the discovered reaction pathway-that is, the stepwise formation of PC and OB bonds-is that the environment (typical organic solvents) stabilizes an intermediate which results from nucleophilic attack of the phosphorus Lewis base on CO2 . This finding is significant because presently the concerted reaction-path paradigm predominates in the rationalization of FLP reactivity. Herein we point out how to attain experimental proof of our results.

The transmetalation is a key elementary step in cross-coupling reactions. Yet, the precise nature of its mechanism and transition state geometry are frequently elusive. This report discloses our study of the transmetalation of [PdII ]-F complexes with the silane- and stannane-based trifluoromethylation agents, R3 SiCF3 and R3 SnCF3 . A divergent reactivity was uncovered, with the stannane showing selective R-group transfer, and the silane selective CF3 -group transfer. Using a combined experimental and computational approach, we uncovered a hitherto unrecognized transmetalation mechanism with the widely employed R3 SiCF3 reagent, explaining its unique activity in metal-catalyzed trifluoromethylations. While the stannane reacts via a cyclic, 4-membered transition state, the silane undergoes a fundamentally different pathway and releases a difluorocarbene in the transmetalation event. Molecular dynamics studies clearly reinforced the liberation of a free CF2 carbene, which reacts with [PdII ]-F to ultimately generate [PdII ]-CF3.

This feature article describes the chemistry in motion of frustrated Lewis pairs (FLPs). With state-of-the-art ab initio molecular dynamics (AIMD) simulations supplemented by minimum energy path (MEP) and potential energy surface (PES) calculations, we examine the binding of CO2 and the heterolytic cleavage of H-2 by a Lewis base (LB), tBu(3)P, and a Lewis acid (LA), B(C6F5)(3). We strive to uncover and understand mechanistic implications of the physical laws that govern the behavior of a LB and a LA when they react with a third species (e.g., CO2 or H-2) at finite temperature. The approximation that we necessarily must make at present is to forgo the quantization of the movement of atoms in favor of the Born-Oppenheimer molecular dynamics (BOMD), which unfold according to the classical (Newton's) laws of motion. However, strict quantum chemical theory is used to compute all of the forces that govern the dynamics of the macromolecular FLP system. Using physical reasoning and innovative computer simulations, we show that multi-scale motion is the predominant mechanistic aspect in reactions of the tBu(3)P/B(C6F5)(3) FLP, as well as, conceivably, those of other similar intermolecular FLPs. Insight achieved thus far leads to a novel activity model for intermolecular FLPs and specific predictions, which could be useful for future experimental and theoretical studies of FLP and other chemistries.

While thiophosgene finds widespread usage on a multi-ton scale, its fluorinated counterpart S=CF

Using Born-Oppenheimer molecular dynamics (BOMD) with density functional theory, transition-state (TS) calculations, and the quantitative energy decomposition analysis (EDA), we examined the mechanism of H

We investigate the transition-state (TS) region of the potential energy surface (PES) of the reaction tBu3P + H2 + B(C6F5)3 → tBu3P-H(+) + (-)H-B(C6F5)3 and the dynamics of the TS passage at room temperature. Owing to the conformational inertia of the phosphane⋅⋅⋅borane pocket involving heavy tBu3P and B(C6F5)3 species and features of the PES E(P⋅⋅⋅H, B⋅⋅⋅H | B⋅⋅⋅P) as a function of P⋅⋅⋅H, B⋅⋅⋅H, and B⋅⋅⋅P distances, a typical reactive scenario for this reaction is a trajectory that is trapped in the TS region for a period of time (about 350 fs on average across all calculated trajectories) in a quasi-bound state (scattering resonance). The relationship between the timescale of the TS passage and the effective conformational inertia of the phosphane⋅⋅⋅borane pocket leads to a prediction that isotopically heavier Lewis base/Lewis acid pairs and normal counterparts could give measurably different reaction rates. Herein, the predicted quasi-bound state could be verified in molecular collision experiments involving femtosecond spectroscopy.

The role of the intra- and intermolecular motion, i.e., molecular vibrations and the relative motion of reactants, remains largely unexplored in the frustrated Lewis acid/base chemistry. Here, we address the issue with the ab initio molecular dynamics (AIMD) study of CO2 binding by a Lewis acid (LA) and a Lewis base (LB), i.e., tBu3P + CO2 + B(C6F5)3 → tBu3P–C(O)O–B(C6F5)3 ([1]). Reasonably large ensemble of AIMD trajectories propagated at 300 K from structures in the saddle region as well as trajectories propagated directly from the reactants region revealed an effect arising from significant recrossing of the saddle area. The effect is that transient complexes composed of weakly interacting reactants nearly cease to progress along the segment of the minimum energy pathway (MEP) at the saddle region for a (subpicosecond) period of time during which the dominant factor is the light-to-heavy type of relative motion of the vibrating reactants, i.e., the “bouncing”-like movement of CO2 with respect to much h...

Binding of CO2 by a Mes(2)PCH(2)CH(2)B(C6F5)(2) Species : An Involvement of the Ground State Species in a Low-Energy Pathway

Using the reaction-relevant two-dimensional potential energy surface, an accurate reaction-pathway mapping and ab inito molecular dynamics, it is shown that CO2 capture by P(tBu)(3) and B(C6F5)(3) ...

Using the combinations of imidazole and dimethyl sulfoxide (DMSO) as axial ligands and 2,2'-bipyridine-6,6'-dicarboxylate (bda) as the equatorial ligand, we have synthesized six novel ruthenium complexes with noticeably different activity as water oxidation catalysts (WOCs). In four C(s) symmetric Ru(II)(κ(3)-bda)(DMSO)L(2) complexes L = imidazole (1), N-methylimidazole (2), 5-methylimidazole (3), and 5-bromo-N-methylimidazole (4). Additionally, in two C(2v) symmetric Ru(II)(κ(4)-bda)L(2) complexes L = 5-nitroimidazole (5) and 5-bromo-N-methylimidazole (6), that is, fully equivalent axial imidazoles. A detailed characterization of all complexes and the mechanistic investigation of the catalytic water oxidation have been carried out with a number of experimental techniques, that is, kinetics, electrochemistry and high resolution mass spectrometry (HR-MS), and density functional theory (DFT) calculations. We have observed the in situ formation of a Ru(II)-complex with the accessible seventh coordination position. The measured catalytic activities and kinetics of complex 1-6 revealed details about an important structure-activity relation: the connection between the nature of axial ligands in the combination and either the increase or decrease of the catalytic activity. In particular, an axial DMSO group substantially increases the turnover frequency of WOCs reported in the article, with the ruthenium-complex having one axial 5-bromo-N-methyl-imidazole and one axial DMSO (4), we have obtained a high initial turnover frequency of ∼180 s(-1). DFT modeling of the binuclear reaction pathway of the O-O bond formation in catalytic water oxidation further corroborated the concept of the mechanistic significance of the axial ligands and rationalized the experimentally observed difference in the activity of complexes with imidazole/DMSO and imidazole/imidazole combinations of axial ligands.

The known ( η 3 -C 3 H 5 ) 2 Fe 2 (CO) 6 is an interesting unbridged “fragile dimer” having an unusually long ∼3.1 A Fe–Fe bond, which readily breaks to form paramagnetic (C 3 H 5 )Fe(CO) 3 monomers. Theoretical studies confirm this experimental ( η 3 -C 3 H 5 ) 2 Fe 2 (CO) 6 structure but also predict higher energy ( η 3 -C 3 H 5 ) 2 Fe 2 (CO) 4 (μ-CO) 2 structures with two bridging carbonyl groups and Fe 2 ( η 3 -μ-C 3 H 5 ) 2 (CO) 6 structures with two bridging allyl groups. For the pentacarbonyl (C 3 H 5 ) 2 Fe 2 (CO) 5 low energy structures with four-electron donor bridging CO groups and structures with Fe Fe formal double bonds are both found. Both types of structures satisfy the 18-electron rule. The lowest energy structures for the tetracarbonyl (C 3 H 5 ) 2 Fe 2 (CO) 4 have Fe–Fe single bonds and obvious gaps in the iron coordination spheres consistent with an iron 16-electron configuration. However, a higher energy (C 3 H 5 ) 2 Fe 2 (CO) 4 structure is found with the short (∼2.3 A) formal Fe Fe triple bond predicted by the 18-electron rule. Carbonyl-rich (C 3 H 5 ) 2 Fe 2 (CO) n ( n = 7, 8) structures are found having monohapto allyl ligands. However, such structures have relatively low carbonyl dissociation energies to give the experimentally known ( η 3 -C 3 H 5 ) 2 Fe 2 (CO) 6 and thus are not likely to be viable candidates for experimental realization under normal conditions.

This feature article describes the chemistry in motion of frustrated Lewis pairs (FLPs). With state-of-the-art ab initio molecular dynamics (AIMD) simulations supplemented by minimum energy path (MEP) and potential energy surface (PES) calculations, we examine the binding of CO2 and the heterolytic cleavage of H-2 by a Lewis base (LB), tBu(3)P, and a Lewis acid (LA), B(C6F5)(3). We strive to uncover and understand mechanistic implications of the physical laws that govern the behavior of a LB and a LA when they react with a third species (e.g., CO2 or H-2) at finite temperature. The approximation that we necessarily must make at present is to forgo the quantization of the movement of atoms in favor of the Born-Oppenheimer molecular dynamics (BOMD), which unfold according to the classical (Newton's) laws of motion. However, strict quantum chemical theory is used to compute all of the forces that govern the dynamics of the macromolecular FLP system. Using physical reasoning and innovative computer simulations, we show that multi-scale motion is the predominant mechanistic aspect in reactions of the tBu(3)P/B(C6F5)(3) FLP, as well as, conceivably, those of other similar intermolecular FLPs. Insight achieved thus far leads to a novel activity model for intermolecular FLPs and specific predictions, which could be useful for future experimental and theoretical studies of FLP and other chemistries.

Using Born-Oppenheimer molecular dynamics (BOMD) with density functional theory, transition-state (TS) calculations, and the quantitative energy decomposition analysis (EDA), we examined the mechanism of H2-liberation from LB—H(+) + (−)H—LA ion-pair, 1, in which the Lewis base (LB) is (o-C6H4Me)3P and the Lewis acid (LA) is B(p-C6F4H)3. BOMD simulations indicate that the path of H2 liberation from the ion-pair 1 goes via the short-lived transient species, LB⋯H2⋯LA, which are structurally reminiscent of the TS-structure in the minimum-energy-path describing the reversible reaction between H2 and (o-C6H4Me)3P/B(p-C6F4H)3 frustrated Lewis pair (FLP). With electronic structure calculations performed on graphics processing units, our BOMD data-set covers more than 1 ns of evolution of the ion-pair 1 at temperature T ≈ 400 K. BOMD simulations produced H2-recombination events with various durations of H2 remaining fully recombined as a molecule within a LB/LA attractive “pocket”—from very short vibrational-time ...

With the help of state-of-the-art ab initio molecular dynamics methods, we investigated the reaction pathway of the {tBu3 P + H2 + B(C6 F5 )3 } system at the mesoscopic level. It is shown that: i) the onset of H2 activation is at much larger boron⋅⋅⋅phosphorus distances than previously thought; ii) the system evolves to the product in a roaming-like fashion because of quasi-periodic nuclear motion along the asymmetric normal mode of P⋅⋅⋅HH⋅⋅⋅B fragment; iii) transient configurations of a certain type are present despite structural interference from the solvent; iv) transient-state configurations with sub-picosecond lifetime have potentially interesting infrared activity in the organic solvent (toluene) as well as in the gas phase. The presented results should be helpful for future experimental and theoretical studies of frustrated Lewis pair (FLP) activity.

The role of the intra- and intermolecular motion, i.e., molecular vibrations and the relative motion of reactants, remains largely unexplored in the frustrated Lewis acid/base chemistry. Here, we address the issue with the ab initio molecular dynamics (AIMD) study of CO2 binding by a Lewis acid (LA) and a Lewis base (LB), i.e., tBu3P + CO2 + B(C6F5)3 → tBu3P-C(O)O-B(C6F5)3 ([1]). Reasonably large ensemble of AIMD trajectories propagated at 300 K from structures in the saddle region as well as trajectories propagated directly from the reactants region revealed an effect arising from significant recrossing of the saddle area. The effect is that transient complexes composed of weakly interacting reactants nearly cease to progress along the segment of the minimum energy pathway (MEP) at the saddle region for a (subpicosecond) period of time during which the dominant factor is the light-to-heavy type of relative motion of the vibrating reactants, i.e., the "bouncing"-like movement of CO2 with respect to much heavier phosphine and borane as main contributor to the mode that is perpendicular to the MEP-direction. In terms of how P···C and B···O distances change with time, the roaming-like patterns of typical AIMD trajectories, reactive and nonreactive alike, extend far beyond the saddle region. In addition to the dynamical portrayal of [1], we provide the energy-landscape perspective that takes into account the hierarchy of time scales. The verifiable implication of the effect found here is that the isotopically substituted (heavier) LB/LA "pair" should be less reactive that the "normal" and thus lighter counterpart.

Activation of H2 by a “frustrated Lewis pair” (FLP) composed of B(C6F5)3 and P(tBu)3 species has been explored with high level direct ab initio molecular dynamics (AIMD) simulations at finite temperature (T = 300 K) in gas phase. The initial geometrical conditions for the AIMD trajectory calculations, i.e., the near attack conformations of FLP + H2, were devised using the host-guest model in which suitable FLP conformations were obtained from the dynamics of the B(C6F5)3/P(tBu)3 pair in gas phase. AIMD trajectory calculations yielded microscopic insight into effects which originate from nuclear motion in the reacting complex, e.g., the alternating compression/elongation of the boron-phosphorous distance and the change of the pyramidality of boron in B(C6F5)3. The ensemble averaged trajectory analysis has been compared with the minimum energy path (MEP) description of the reaction. Similar to MEP, AIMD shows that an attack of the acid/base pair on the H–H bond gives rise to the polarization of the H2 molecule and as a consequence generates a large dipole moment of the reacting complex. The MEP and AIMD portrayals of the reaction are fundamentally different in terms of the magnitude of the motion of nuclei in B(C6F5)3 and P(tBu)3 during the H2 cleavage. In the AIMD trajectory simulations, geometries of B(C6F5)3 and P(tBu)3 appear as nearly “frozen” on the short time scale of the H2 cleavage. This is contrary to the MEP picture. Several of the concepts which arise from this work, e.g., separation of time scales of nuclear motion and the time-dependence of the donor-acceptor interactions in the reacting complex, are important for the understanding of chemical reactivity and catalysis.

A number of evanescent unsubstituted homoleptic allyl derivatives M(C(3)H(5))(n) of the first row transition metals have been reported in the literature. In addition, the much more thermally stable silylated derivatives M[C(3)H(3)(SiMe(3))(2)](2) (M = Cr, Fe, Co, Ni) are reported to survive vacuum sublimation without significant decomposition. In this connection, the complete series of homoleptic allyl derivatives M(C(3)H(5))(n) (n = 2, 3; M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni) have been studied theoretically using density functional theory. In most of the lowest energy predicted M(C(3)H(5))(n) structures all of the allyl groups are bonded as trihapto η(3)-C(3)H(5) ligands and the metals have considerably less than the normally favored 18-electron configuration. Such ligands can be considered formally as bidentate ligands with the metal atom connected to the centers of the two C-C bonds of the η(3)-C(3)H(5) group. The later transition metal diallyls M(C(3)H(5))(2) (M = Cr, Mn, Fe, Co, Ni) form two stereoisomers of similar relative energies, namely the C(2h) staggered isomer and the C(2v) eclipsed isomer with the orientation of the η(3)-C(3)H(5) groups corresponding to square planar metal coordination of the bidentate η(3)-C(3)H(5) ligands. The staggered and eclipsed Ni(C(3)H(5))(2) isomers have been observed experimentally by NMR. Less symmetrical M(C(3)H(5))(2) structures are found for the earlier transition metals Sc, Ti, and V in which the orientation of the allyl groups corresponds to tetrahedral metal coordination. The triallylmetal derivatives M(C(3)H(5))(3) are predicted to be thermodynamically viable with respect to allyl loss to give the corresponding diallylmetal derivatives, except for triallylnickel. The lowest energy Ni(C(3)H(5))(3) structure has two trihaptoallyl ligands and one monohaptoallyl ligand, whereas the lowest energy Mn(C(3)H(5))(3) structures have only one trihaptoallyl ligand and two monohaptoallyl ligands. Otherwise, the M(C(3)H(5))(3) complexes have structures with three trihaptoallyl ligands corresponding formally to octahedral metal coordination. The M(C(3)H(5))(3) complexes (M = Cr, Co) thus correspond to a well-known series of "classical" octahedral coordination complexes, namely, those of the d(3) Cr(III) and the d(6) Co(III), respectively.