Biomimics of [FeFe]-hydrogenases with a pendant amine: Diphosphine complexes [Fe₂(CO)₄{μ-S(CH₂)nS}{κ²-(Ph₂PCH₂)₂NR}] (n = 2, 3; R = Me, Bn) towards H₂ oxidation catalysts

We report the synthesis and molecular structures of [FeFe]-ase biomimics [Fe2(CO)4{µ-S(CH2)nS}{κ2-(Ph2PCH2)2NR}] (1–4) (n = 2, 3; R = Me, Bn) and a comparative study of their protonation and redox chemistry, with the aim of assessing their activity as catalysts for H2 oxidation. They are prepared in good yields upon heating the hexacarbonyls and PCNCP ligands in toluene, a minor product of one reaction (n = 3, R = Bn) being pentacarbonyl [Fe2(CO)5(µ-pdt){Ph2PCH2N(H)Bn}] (5). Crystal structures show short Fe-Fe bonds (ca. 2.54 Å) with the diphosphine occupying basal-apical sites. Each undergoes a quasi-reversible one-electron oxidation and IR-SEC shows that this results in formation of a semi-bridging carbonyl. As has previously been observed, protonation products are solvent dependent, nitrogen being the favoured site of protonation site upon addition of one equivalent of HBF4.Et2O in d6-acetone, while hydride formation is favoured in CD2Cl2. However, the rate of N to Fe2 proton-transfer varies greatly with the nature of both the dithiolate-bridge and amine-substituent. Thus with NMe complexes (1–2) N-protonation is favoured in acetone affording a mixture of endo and exo isomers, while for NBn complexes (3–4) proton-transfer to afford the corresponding μ-hydride occurs in part (for 3 edt) or exclusively (for 4 pdt). In acetone, addition of a further equivalent of HBF4.Et2O generally does not lead to hydride formation, but in CD2Cl2 dications [Fe2(CO)4{µ-S(CH2)nS}(μ-H){κ2-(Ph2PCH2)2NHR}]2+ result, in which the diphosphine can adopt either dibasal or basal-apical positions. Proton-transfer from Fe2 to N has been previously identified as a required transformation for H2 oxidation, as has the accessibility of the all-terminal carbonyl isomer of cations [Fe2(CO)4{µ-S(CH2)nS}{κ2-(Ph2PCH2)2NR}]+. We have carried out a preliminary H2 oxidation study of 3, oxidation by Fc[BF4] in the presence of excess P(o-tolyl)3 affording [HP(o-tol)3][BF4], with a turnover of ca. 2.3 ± 0.1 mol of H2 consumed per mole of

Biomimics of [FeFe]-hydrogenases with a pendant amine:Diphosphine complexes [Fe₂(CO)₄{µ-S(CH₂)_nS}{κ²-(Ph₂PCH₂)₂NR}] (n = 2, 3; R = Me, Bn) towards H₂ oxidation catalysts

We report the synthesis and molecular structures of [FeFe]-ase biomimics [Fe 2 (CO) 4 {μ-S(CH 2 ) n S}{ κ2 - (Ph 2 PCH 2 ) 2 NR}] ( 1–4 ) ( n = 2, 3; R = Me, Bn) and a comparative study of their protonation and re- dox chemistry, with the aim of assessing their activity as catalysts for H 2 oxidation. They are prepared in good yields upon heating the hexacarbonyls and PCNCP ligands in toluene, a minor product of one reaction ( n = 3, R = Bn) being pentacarbonyl [Fe 2 (CO) 5 (μ-pdt){Ph 2 PCH 2 N(H)Bn}] ( 5 ). Crystal structures show short Fe-Fe bonds (ca. 2.54 ˚A) with the diphosphine occupying basal-apical sites. Each undergoes a quasi-reversible one-electron oxidation and IR-SEC shows that this results in formation of a semi-bridging carbonyl. As has previously been observed, protonation products are solvent dependent, nitrogen being the favoured site of protonation site upon addition of one equivalent of HBF 4 .Et 2 O in d 6 -acetone, while hydride formation is favoured in CD 2 Cl 2 . However, the rate of N to Fe 2 proton-transfer varies greatly with the nature of both the dithiolate-bridge and amine-substituent. Thus with NMe complexes ( 1–2 ) N- protonation is favoured in acetone affording a mixture of endo and exo isomers, while for NBn complexes ( 3–4 ) proton-transfer to afford the corresponding μ-hydride occurs in part (for 3 edt) or exclusively (for 4 pdt). In acetone, addition of a further equivalent of HBF 4 .Et 2 O generally does not lead to hydride for- mation, but in CD 2 Cl 2 dications [Fe 2 (CO) 4 {μ-S(CH 2 ) n S}( μ-H){ κ2 -(Ph 2 PCH 2 ) 2 NHR}] 2 + result, in which the diphosphine can adopt either dibasal or basal-apical positions. Proton-transfer from Fe 2 to N has been previously identified as a required transformation for H 2 oxidation, as has the accessibility of the all- terminal carbonyl isomer of cations [Fe 2 (CO) 4 {μ-S(CH 2 ) n S}{ κ2 -(Ph 2 PCH 2 ) 2 NR}] + . We have carried out a preliminary H 2 oxidation study of 3, oxidation by Fc[BF 4 ] in the presence of excess P(o-tolyl) 3 affording [HP(o-tol) 3 ][BF 4 ], with a turnover of ca. 2.3 ±0.1 mol of H 2 consumed per mole of 3

PCP complexes of Titanium in the +3 and +4 oxidation states

Ti(IV) and Ti(III) complexes using the tBuPCP ligand have been synthesized (tBuPCP = C6H3-2,6-(CH2PtBu2)2). The [tBuPCP]Li synthon can be reacted with TiCl4(THF)2 to form (tBuPCP)TiCl3 (1) in limited yields due to significant reduction of the titanium synthon. The Ti(III) complex (tBuPCP)TiCl2 (2) has been further characterized. This can have half an equivalent of halide abstracted to form [{(tBuPCP)TiCl}2{μ-Cl}][B(C6F5)4] (3) and can also be methylated, forming (tBuPCP)TiMe2 (4). All the Ti(III) complexes have been characterized using EPR and X-ray crystallography, giving insight into their electronic structures, which are further supported by DFT calculations

PCP Complexes of Titanium in the +3 and +4 Oxidation State

Ti(IV) and Ti(III) complexes using the tBuPCP ligand have been synthesised (tBuPCP = C6H3-2,6-(CH2PtBu2)2). The [tBuPCP]Li synthon can be reacted with TiCl4(THF)2 to form (tBuPCP)TiCl3 (1) in limited yields due to significant reduction of the titanium synthon. The Ti(III) complex (tBuPCP)TiCl2 (2) has been further characterised. This can have half an equivalent of halide abstracted to form [{(tBuPCP)TiCl}2{μ-Cl}][B(C6F5)4] (3) and can also be methylated forming (tBuPCP)TiMe2 (4). All the Ti(III) complexes have been characterised using EPR and x-ray crystallography, giving insight into their electronic structure, which is further supported by DFT calculations