There is considerable interest in both catalysts for CO(2) conversion and understanding how CO(2) reacts with transition metal complexes. Here we develop a simple model for predicting the thermodynamic favorability of CO(2) insertion into Ir(III) hydrides. In general this reaction is unfavorable; however, we demonstrate that with a hydrogen bond donor in the secondary coordination sphere it is possible to isolate a formate product from this reaction. Furthermore, our CO(2) inserted product is one of the most active water-soluble catalysts reported to date for CO(2) hydrogenation.
The reactions of PCP supported Ni hydride, methyl and allyl species with CO(2) to generate Ni carboxylates are described. Computational studies suggest that all three reactions follow different pathways.
The preparation of a number of iron complexes supported by ligands of the type HN{CH2CH2(PR2)}2 [R = isopropyl (((i)Pr)PNP) or cyclohexyl ((Cy)PNP)] is reported. This is the first time this important bifunctional ligand has been coordinated to iron. The iron(II) complexes (((i)Pr)PNP)FeCl2(CO) (1a) and ((Cy)PNP)FeCl2(CO) (1b) were synthesized through the reaction of the appropriate free ligand and FeCl2 in the presence of CO. The iron(0) complex (((i)Pr)PNP)Fe(CO)2 (2a) was prepared through the reaction of Fe(CO)5 with ((i)Pr)PNP, while irradiating with UV light. Compound 2a is unstable in CH2Cl2 and is oxidized to 1a via the intermediate iron(II) complex [(((i)Pr)PNP)FeCl(CO)2]Cl (3a). The reaction of 2a with HCl generated the related complex [(((i)Pr)PNP)FeH(CO)2]Cl (4a), while the neutral iron hydrides (((i)Pr)PNP)FeHCl(CO) (5a) and ((Cy)PNP)FeHCl(CO) (5b) were synthesized through the reaction of 1a or 1b with 1 equiv of (n)Bu4NBH4. The related reaction between 1a and excess NaBH4 generated the unusual η(1)-HBH3 complex (((i)Pr)PNP)FeH(η(1)-HBH3)(CO) (6a). This complex features a bifurcated intramolecular dihydrogen bond between two of the hydrogen atoms associated with the η(1)-HBH3 ligand and the N-H proton of the pincer ligand, as well as intermolecular dihydrogen bonding. The protonation of 6a with 2,6-lutidinium tetraphenylborate resulted in the formation of the dimeric complex [{(((i)Pr)PNP)FeH(CO)}2(μ2,η(1):η(1)-H2BH2)][BPh4] (7a), which features a rare example of a μ2,η(1):η(1)-H2BH2 ligand. Unlike all previous examples of complexes with a μ2,η(1):η(1)-H2BH2 ligand, there is no metal-metal bond and additional bridging ligand supporting the borohydride ligand in 7a; however, it is proposed that two dihydrogen-bonding interactions stabilize the complex. Complexes 1a, 2a, 3a, 4a, 5a, 6a, and 7a were characterized by X-ray crystallography.
A series of Ni(II) and Pd(II) hydrides supported by PNP and PCP ligands, including iPr2 PNP (CH3) PdH ( iPr2 PNP (CH3) = N(2-P i Pr 2 -4-MeC 6 H 3 ) 2 ), iPr2 PNP (CH3) NiH, iPr2 PNP (F) PdH ( iPr2 PNP (F) = N(2-P i Pr 2 -4-C 6 H 3 F) 2 ), CyPh PNPPdH ( CyPh PNP = N(2-P(Cy)(Ph)-4-MeC 6 H 3 ) 2 ), tBu2 PCPPdH ( tBu2 PCP = 2,6-C 6 H 3 (CH 2 P t Bu 2 ) 2 ), tBu2 PCPNiH, Cy2 PCPPdH ( Cy2 PCP = 2,6-C 6 H 3 (CH 2 PCy 2 ) 2 ), and Cy2 PCPNiH, were prepared using literature methods. In addition, the new Ni and Pd hydrides Cy2 PSiPMH (M = Ni, Pd; Cy2 PSiP = Si(Me)(2-PCy 2 -C 6 H 4 ) 2 ) supported by PSiP ligands were synthesized. The analogous metal hydride complexes supported by the Ph2 PSiP ligand ( Ph2 PSiP = Si(Me)(2-PPh 2 -C 6 H 4 ) 2 ) could not be prepared. Instead, the Ni(0) and Pd(0)which have been proposed to be in equilibrium with Ph2 PSiPMH (M = Ni, Pd) and PPh 3 , were prepared. Facile carbon dioxide insertion into the metal−hydride bond to form the metal formate complexes tBu2 PCPM-OC(O)H (M = Ni, Pd) or Cy2 PCPM-OC(O)H (M = Ni, Pd) was observed for PCP-supported species, and a similar reaction was observed for Cy2 PSiP-supported hydrides to form Cy2 PSiPM-OC(O)H (M = Ni, Pd).No reaction with carbon dioxide was observed for any complexes supported by PNP ligands. The η 2 -silane complex Ph2 PSi H PPd(PPh 3 ) reacted rapidly with carbon dioxide to give Ph2 PSiPPd-OC(O)H and PPh 3 , while the corresponding Ni complex Ph2 PSi H PNi(PPh 3 ) did not react with carbon dioxide. DFT calculations indicate that carbon dioxide insertion is thermodynamically favorable for PSiP-and PCP-supported hydrides because the strong trans influence of the anionic carbon donor destabilizes the metal−hydride bond. In contrast, carbon dioxide insertion is thermodynamically unfavorable for the PNP-supported species. In the case of the η 2 -silane complexes, carbon dioxide insertion is thermodynamically favorable for Pd and unfavorable for Ni. This is because the equilibrium between the metal hydride and PPh 3 and the η 2 -silane complex more strongly favors the metal hydride for Pd than for Ni. In the cases of metal hydrides, the thermodynamic favorability of carbon dioxide insertion can be predicted from the natural bond orbital charge on the hydride. The pathway for carbon dioxide insertion into the metal hydride is concerted and features a four-centered transition state. The energy of the transition state for carbon dioxide insertion decreases as the trans influence of the anionic donor of the pincer ligand increases.
The Ni amide and hydroxide complexes [(PCP)Ni(NH(2))] (2; PCP=bis-2,6-di-tert-butylphosphinomethylbenzene) and [(PCP)Ni(OH)] (3) were prepared by treatment of [(PCP)NiCl] (1) with NaNH(2) or NaOH, respectively. The conditions for the formation of 3 from 1 and NaOH were harsh (2 weeks in THF at reflux) and a more facile synthetic route involved protonation of 2 with H(2)O, to generate 3 and ammonia. Similarly the basic amide in 2 was protonated with a variety of other weak acids to form the complexes [(PCP)Ni(2-Me-imidazole)] (4), [(PCP)Ni(dimethylmalonate)] (5), [(PCP)Ni(oxazole)] (6), and [(PCP)Ni(CCPh)] (7), respectively. The hydroxide compound 3, could also be used as a Ni precursor and treatment of 3 with TMSCN (TMS=trimethylsilyl) or TMSN(3) generated [(PCP)Ni(CN)] (8) or [(PCP)Ni(N(3))] (9), respectively. Compounds 3-7, and 9 were characterized by X-ray crystallography. Although 3, 4, 6, 7, and 9 are all four-coordinate complexes with a square-planar geometry around Ni, 5 is a pseudo-five-coordinate complex, with the dimethylmalonate ligand coordinated in an X-type fashion through one oxygen atom, and weakly as an L-type ligand through another oxygen atom. Complexes 2-9 were all reacted with carbon dioxide. Compounds 2-4 underwent facile reaction at low temperature to form the κ(1)-O carboxylate products [(PCP)Ni{OC(O)NH(2)}] (10), [(PCP)Ni{OC(O)OH}] (11), and [(PCP)Ni{OC(O)-2-Me-imidazole}] (12), respectively. Compounds 10 and 11 were characterized by X-ray crystallography. No reaction was observed between 5-9 and carbon dioxide, even at elevated temperatures. DFT calculations were performed to model the thermodynamics for the insertion of carbon dioxide into 2-9 to form a κ(1)-O carboxylate product and understand the pathways for carbon dioxide insertion into 2, 3, 6, and 7. The computed free energies indicate that carbon dioxide insertion into 2 and 3 is thermodynamically favorable, insertion into 8 and 9 is significantly uphill, insertion into 5 and 7 is slightly uphill, and insertion into 4 and 6 is close to thermoneutral. The pathway for insertion into 2 and 3 has a low barrier and involves nucleophilic attack of the nitrogen or oxygen lone pair on electrophilic carbon dioxide. A related stepwise pathway is calculated for 7, but in this case the carbon of the alkyne is significantly less nucleophilic and as a result, the barrier for carbon dioxide insertion is high. In contrast, carbon dioxide insertion into 6 involves a single concerted step that has a high barrier.
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