PN³(P)-Pincer Complexes: Cooperative Catalysis and Beyond

An Update on Formic Acid Dehydrogenation by Homogeneous Catalysis

“…In 2011, Nozaki and co-workers first investigated the PNP-ligated iridium trihydride complex 13 dehydrogenation behavior in the idea of reversible H 2 fixation, and the H 2 gas was measured by water replacement to provide a TON of 890 (Figure 7). [8a] As the hydrogen transfer of ketones was demonstrated using the RuÀ PN 3 (P) pincer complexes, [35] it was not a surprise that the FA dehydrogenation could also proceed. [9m,r,36] This well-defined PN 3 -Pincer Ru catalytic system (14) can efficiently and selectively liberate H 2 from FA under mild conditions without CO and reached a TOF of 7,000 h À 1 and a TON more than 1.1 million during a long lifetime over 150 hours.…”

Ru(II)‐PBTNNXN complex bearing functional 2‐(pyridin‐2‐yl)benzo[d]thiazole ligand catalyzed α‐alkylation of nitriles with alcohols

“…[13] Kundu and co-workers demonstrated that Ru complexes bearing N6,N6 0 -dimethyl-2,2'-bipyridine-6,6'diamine ligand efficiently catalyzed α-alkylation of arylacetonitriles with alcohols. [14] Recently, Ru catalyst based on tridentate bipyridyl imidazoline catalyzed analogous reaction was reported by Song et al [15] Metal-ligand cooperation (MLC) [27][28][29][30][31][32] plays an important role in catalysis. It can dramatically promote the catalytic activity applied in borrowing hydrogen catalysis using ligands containing functional groups such as NH [33][34][35][36][37] and OH [38][39][40] .…”

“…This has potential benefits for electronic transfer, which is important for metal-ligand cooperation. [27,28] The color-tuning of iridium complexes bearing 2-phenylbenzothiazole ligands has been achieved by changing the chromophore and/or groups on the benzothiazole moiety and/or phenyl ring, implying their prior properties for easy structural modification and tuneable electronic effect. [50][51][52][53] The catalytic activity for Suzuki cross-coupling of Pd (SCN) pincer complexes supported by thiophosphoryl-benzothiazole ligand is deeply influenced by the attached substituent group, suggesting that they could adjust catalytic reactivity.…”

Visible‐Light Photocatalytic Reduction of CO2 to Formic Acid with a Ru Catalyst Supported by N,N′‐Bis(diphenylphosphino)‐2,6‐diaminopyridine Ligands

“…Furthermore, formic acid has been identified and explored as ap otential carrier of dihydrogen. [24][25][26] Furthermore, the potentialo fp incerc omplexes as efficient electrocatalysts for CO 2 reduction under mild conditions has recently been demonstrated for Mn, [27] Ru, [28] and Ir [29,30] complexes. [3][4][5][6] Photocatalysis is ap articularly appealing approacha s it relies on an essentially limitless and clean solar energy source.P hotocatalytic systemsc onsisto fi ntegrated components that include ap hotosensitizer (PS)f or harvesting the energy of the light, an electron donor (ED)t hat provides electrons for the reduction, and ac atalyst (CAT)t hat is as ite for the transformation of CO 2 .T oo ur knowledge,s ince their discovery in 1985, [7] all of the reported molecular photocatalysts based on Ru II have used a-diimine supporting ligandsa nd these speciesh ave fallen into two broad groups.O ne class are bis(a-diimine) speciesr epresentedb ycis-[Ru(N^N) 2 (CO) 2 ] 2 + [8][9][10][11] and the other are mono(a-diimine) catalysts represented by cis,trans-[Ru(N^N)(CO) 2 Cl 2 ].…”

“…[1,2] Homogeneous catalysts have been developed for CO 2 reduction under both electrochemical and photochemical conditions. [24][25][26] Furthermore, the potentialo fp incerc omplexes as efficient electrocatalysts for CO 2 reduction under mild conditions has recently been demonstrated for Mn, [27] Ru, [28] and Ir [29,30] complexes. [12][13][14] Althoughavariety of substituents on the a-diimine ligands have been productively explored to improvec atalystp erformance, given the maturity of this field, ab roader variationo fm olecular architecture is required to provide new insights and stimulate new concepts in this field.…”