N-Acyclic carbene complexes supported by meso-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (meso-dpmppm) as an asymmetric pincer ligand

An Electrophilic, Intramolecularly Base-Stabilized Platinum–Antimony Complex

“…This slight elongation suggests that the neutral cyclohexyl isocyanide ligand has a stronger trans influence than the anionic chloride ligand. While we have not found a clearly stated precedent for this interpretation, related observations have been made in the case of complexes D and E recently described by Tanase et al, who observed that displacement of the platinum-bound chloride by a cyclohexyl isocyanide ligand leads to a noticeable lengthening of the Pt–P bond trans from the isocyanide ligand . The phosphine oxide functionality remains coordinated to the antimony center, as indicated by an O–Sb separation of 2.543(2) Å, which only slightly exceeds that of [ 2 –Cl] + (2.432(4) Å).…”

Synthesis of Cu(II) complexes by N,O‐donor ligand transformation and their catalytic role in visible‐light‐driven alcohol oxidation

“…A flexible ring or open structure as ligand with one or more than one donor centers can induce structural preferences in formation of metal complexes in various ways. [1][2][3][4][5][6] It has been also noticed that in a sterically demanding situation or for the sake of less strainer chelating environment, certain ligands can decyclise or ring-opening of the ligands can happen. [7][8][9][10][11][12][13][14][15] In point of view of the catalytic properties, in-built flexibility of the associated ligands in terms of denticity, ability to engage in different noncovalent interactions with substrate, and providing an efficient and robust platform remain very crucial as per earlier reports.…”

Dinuclear Copper Complexes Triply Bridged by a Tetraphosphane, rac‐Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2

“…Multinuclear transition‐metal complexes have extensively been studied to explore new aspects of functional materials because a variety of synergistic effects in multimetallic centers are expected to play key roles in developing catalytic systems, electronic, optical, and magnetic devices, and biomimetic functional molecules . To create desired multinuclear centers, design of multidentate metal supporting ligands is very important issue, and in this regard, we have prepared a methylene‐bridged linear tetraphosphane, meso ‐ and rac ‐bis[(diphenylphosphinomethyl)phenylphosphino]methane (dpmppm), and demonstrated that it effectively stabilized versatile tetra‐, tri‐, and dinuclear homo and heterometallic systems as well as mononuclear centers (Scheme ) . First of all, meso ‐ and rac ‐dpmppm preferably supported linearly ordered tetranuclear metal centers in κ 1 ,κ 1 ,κ 1 ,κ 1 coordination mode (Scheme a, Scheme f), exemplified by the linear octapalladium rigid‐rods, [Pd 8 ( meso ‐ or rac ‐dpmppm) 4 L 2 ] 4+ (L = none, MeCN, N , N ‐dimethylformamide (dmf), and isocyanides),, which dissociate at higher temperature T > 100 °C into two tetrapalladium units of {Pd 4 ( meso ‐ or rac ‐dpmppm) 2 } 2+ and interestingly they are self‐aligned at lower temperature T < 60 °C to restore the original rods through asymmetric recognition between the tetrapalladium units .…”

“…The meso ‐dpmppm ligand was found to surround a Pd II or Pt II mononuclear center in a pincer‐type κ 3 ‐fashion (Scheme e) affording [MCl(dpmppm‐κ 3 )] + (M = Pt, Pd) that involve fused six‐ and four‐membered chelate rings with an uncoordinated phosphane unit in the six‐membered ring, and are transformed, by addition of Cp*MCl 2 fragment (M = Rh, Ir) onto the uncoordinated phosphane, into [MCl(Cp*M′Cl 2 )(µ‐ meso ‐dpmppm‐κ 3 ,κ 1 )] + (M = Pt, Pd; M′ = Rh, Ir) (Scheme d) , . The PdM′ complex with meso ‐dpmppm‐κ 3 ,κ 1 bridge captured the third metal ion via cleavage of the four‐membered chelate ring to afford heterotrimetallic complexes, [PdCl 2 (Cp*M′Cl 2 )(Cp*MCl 2 )(µ‐ meso ‐dpmppm‐κ 2 ,κ 1 ,κ 1 )] and [PdCl(µ‐Cl)(Cp*M′Cl)(Cp*MCl 2 )(µ‐dpmppm‐κ 2 ,κ 1 ,κ 1 )]PF 6 (M, M′ = Rh, Ir), in stepwise ways (Scheme b) .…”