Fine Tunable, Redox Active Octapalladium Chains Supported by Linear Tetraphosphines, Leading to Dynamically 1D Self‐Assembled Coordination Polymers

Abstract

A series of the octapalladium chains supported by meso‐Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (meso‐dpmppm) ligands, [Pd8(meso‐dpmppm)4(L)2](BF4)4 (L=none (1), solvents: CH3CN (2 a), dmf (2 b), dmso (2 c), RN≡C: R=Xyl (3 a), Mes (3 b), Dip (3 c), tBu (3 d), Cy (3 e), CH3(CH2)7 (3 f), CH3(CH2)11 (3 g), CH3(CH2)17 (3 h)) and [Pd8(meso‐dpmppm)4(X)2](BF4)2 (X=Cl (4 a), N3 (4 b), CN (4 c), SCN (4 d)), were synthesized by using 2 a as a stable good precursor, and characterized by spectroscopic (IR, 1H and 31P NMR, UV‐vis‐NIR, ESI‐MS) measurements and X‐ray crystallographic analyses (for 1, 2 a, b, 3 a, b, e, f, 4 a–d). On the basis of DFT calculations on the X‐ray determined structure of 2 b ([2b‐Pd8]4+) and the optimized models [Pd8(meso‐Ph2PCH2P(H)CH2P(H)CH2PH2)4(CH3CN)2]4+ ([Pd8Ph8]4+) and [Pd8(meso‐H2PCH2P(H)CH2P(H)CH2PH2)4(CH3CN)2]4+ ([Pd8H8]4+), with and without empirically calculating dispersion force stabilization energy (B3LYP‐D3, B3LYP), the formation energy between the two Pd4 fragments is assumed to involve mainly noncovalent interactions (ca. −70 kcal/mol) with four sets of interligand C−H/π interactions and Pd⋅⋅⋅Pd metallophilic one, while electron shared covalent interactions are almost canceled out within the Pd8 chain. All the compounds isolated are stable in solution and exhibit characteristic absorption at ∼900 nm, which is assignable to a spin allowed HOMO to LUMO transition, and shows temperature dependent intensity change with variable absorption coefficients presumably due to coupling with some thermal vibrations. The structures and electronic states of the Pd8 chains are found finely tunable by varying the terminal capping ligands. In particular, theoretical calculations elucidated that the HOMO‐LUMO energy gap is systematically related to the central Pd−Pd distance (2.7319(6)–2.7575(6) Å) by two ways with neutral ligands L (1, 2, 3) and with anionic ligands X (4), which are reflected on the NIR absorption energy of 867–954 nm. The isocyanide terminated Pd8 complexes (3) further reacted with excess of RNC (6 eq) to afford the Pd4 complexes, [Pd4(meso‐dpmppm)2(RNC)2](BF4)2 (13), and the cyclic voltammograms of 2 a (L=CH3CN), 3, and 13 (R=Xyl, Mes, tBu, Cy) demonstrated wide range redox behaviors from 2{Pd4}4+ to 2{Pd4}0 through 2{Pd4}2+↔{Pd8}4+, {Pd8}3+, and {Pd8}2+ strings. The oxidized complexes, [Pd4(meso‐dpmppm)2(RNC)3](BF4)4 (16), were characterized by X‐ray analyses, and the two‐electron reduced chain of [Pd8(meso‐dpmppm)4](BF4)2 (7) was analyzed by spectroscopic and electrochemical techniques and DFT calculations. Reactions of 2 a with 1 equiv. of aromatic linear bisisocyanide (BI) in CH2Cl2 deposited insoluble coordination polymers, {[Pd8(meso‐dpmppm)4(BI)](BF4)4}n (5), and interestingly, they were soluble in acetonitrile, 31P{1H} and 1H DOSY NMR spectra as well as SAXS curves suggesting that the coordination polymers may exist in acetonitrile as dynamically 1D self‐assembled coordination polymers comprising ca. 50 units of the Pd8 rod averaged within the timescale.

Tetranuclear Pd4, PtnPd4‐n (n=1–3), and Pt4 Chains Supported by rac‐ and meso‐Ph2PCH2P(Ph)N(Ar)P(Ph)CH2PPh2 Tuned by Changing N‐Substituents, P‐Configuration, and Terminal Ligands

“…Preparation of [Pd 4 (rac-dpmppan) 2 (XylNC) 2 ](PF 6 ) 2 (1): [10] To an acetonitrile solution (4 mL) containing rac-dpmppan (106.3 mg, 0.151 mmol) were added [Pd 2 (XylNC) 6 ](PF 6 ) 2 (97.1 mg, 75.3 μmol) and [Pd(dba) 2 ] (86.6 mg, 0.151 mmol) successively, and the solution was heated at 60 °C with stirring for 2 h. The resultant dark green solution was concentrated to dryness, and the residue was washed with diethyl ether (1 mL) and extracted with acetonitrile (2 mL) which was filtered. To the extract was carefully added Et 2 O (8 mL) and the mixed solution was kept at À 10 °C to give dark green needle crystals of Preparation of [Pt 2 Pd 2 (rac-dpmppan) 2 (XylNC) 2 ](PF 6 ) 2 (4): [11] To an acetonitrile solution (2 mL) containing [Pt 2 (XylNC) 6 ](PF 6 ) 2 (11.1 mg, 7.57 μmol) was added rac-dpmppan (10.7 mg, 15.2 μmol) dissolved in 100 μL of dichloromethane, and the solution was stirred at room temperature for 4 h, and then [Pd(dba) 2 ] (8.7 mg, 15.1 μmol) and 2 mL of acetonitrile were added.…”

“…[6,7] In particular, meso-and racdpmppm (n = 1) have been demonstrated to effectively support linear metal chains of {Pd 8 (meso-or rac-dpmppm) 4 } 4 + that were generated by self-alignment of two Pd 4 units of {Pd 4 (meso-or rac-dpmppm) 4 } 2 + through chiral recognition. [8][9][10] Recently, a linear tetraphosphine possessing a PN(Ph)P phosphazane bridge, rac-bis[(diphenylphosphinomethyl)phenylphosphino]phenylamine (rac-dpmppan), was synthesized to tune the linear Pd 4 units (Scheme 1). [11] Reaction of racdpmppan with [Pd 2 (XylNC) 6 ](PF 6 ) 2 and [Pd(dba) 2 ] (Xyl = 2,6-xylyl, dba = dibenzalacetone) in 2 : 1 : 2 ratio afforded the Pd 4 chain with XylNC terminal ligands, [Pd 4 (rac-dpmppan) 2 (XylNC) 2 ](PF 6 ) 2 (1), that was interestingly transformed by treating with [Pt 3 (XylNC) 6 ] into [PtPd 3 (rac-dpmppan) 2 (XylNC) 2 ](PF 6 ) 2 (2) and [PtPd 2 Pt(rac-dpmppan) 2 (XylNC) 2 ](PF 6 ) 2 (3), successively.…”

“…With an aim of establishing structurally constrained multinuclear metal units that serve as building blocks for nano‐scaled molecular devices and catalytic centers with metal synergistic effects, [1–5] we have developed linearly ordered tetraphosphines, Ph 2 PCH 2 P(Ph)(CH 2 ) n P(Ph)CH 2 PPh 2 ( n =1–4), as multinuclear supporting ligands [6,7] . In particular, meso ‐ and rac ‐dpmppm ( n =1) have been demonstrated to effectively support linear metal chains of {Pd 8 ( meso ‐ or rac ‐dpmppm) 4 } 4+ that were generated by self‐alignment of two Pd 4 units of {Pd 4 ( meso ‐ or rac ‐dpmppm) 4 } 2+ through chiral recognition [8–10] . Recently, a linear tetraphosphine possessing a PN(Ph)P phosphazane bridge, rac ‐bis[(diphenylphosphinomethyl)phenylphosphino]phenylamine ( rac ‐dpmppan), was synthesized to tune the linear Pd 4 units (Scheme 1).…”

Development of Multinuclear Metal Systems Structurally Constrained by Linear Polyphosphines

“…10 Estimated structural changes of dynamical 1D coordination polymers of {[Pd 8 (meso-dpmppm) 4 (BI)] (BF 4 ) 4 } n(27) to {[Pd 4 (mesodpmppm) 2 (BI)](BF 4 ) 2 } n(28), and finally to network polymers {[Pd 4 (mesodpmppm) 2 (BI) 1.5 ](BF 4 ) 2 } n(29). BI = 2,3,5,6-Me 4 C 6 -1,4-(NC) 2 25.…”

“…Fig 25. Preparations of CuH multinuclear complexes supported by meso/rac-dpmppe, meso-dpmppp, and meso-dpmppb.…”