Routes to dicationic ruthenium(II) nitrile complexes containing chelating diphosphine ligands: X-ray analyses of Ru(dppb)(MeCN)₄²⁺ 2PF₆⁻(dppb = Ph₂P(CH₂)₄PPh₂) and trans-RuCl₂(MeCN)₄

Abstract

Routes to the R U ( P P ) ( R C N )~~+~P F~-C O~~~~X~S(PP = Ph,P(CH,),PPh,, dppb; R =Me, Ph) from the Ru(I1) precursors Ru2CL,(PP), and RuCI,(PP)(PPh,) have been established. The X-ray crystal structure of the dppb-MeCN derivative (3) is described, and the steric effect of the diphosphine ligand is examined by comparison with the crystal structure of trans-RuCI,(MeCN), (5), which is also presented. Crystals of 3 are triclinic, a

Synthesis, Structures, Ligand Substitution Reactions, and Electrochemistry of the Nitrile Complexescis-[Ru(dppm)2Cl(NCR)]+ PF6- (dppm = Bis(diphenylphosphino)methane, R = CH3, C2H5,tBu, Ph)

“…This argues against any significant Ru dp±NºC pp* back bonding in these cationic Ru II complexes. [21]. In the former complex, the Ru±N bonds trans to the diphosphine ligand were found to be considerably longer than those to mu- …”

RuII and RuIII Chloronitrile Complexes: Synthesis, Reaction Chemistry, Solid State Structure, and (Spectro)Electrochemical Behavior

“…Complex 6 is centrosymmetric with two chlorides perpendicular to the Ru(N≡C Ph ) 4 plane. All bond lengths and angles in 6 are comparable to those in trans ‐[RuCl 2 (N≡CMe) 4 ] [ 60,62 ] with no distinguishable differences resulting from the change from acetonitrile to benzonitrile. In the solid state, 6 forms 2D layers due to π‐interactions between the aromatic benzonitrile ligands (Figure 3).…”

“…The average Ru–N and Ru–Cl bond lengths in 4a , b are comparable to those ones found in other ruthenium chloride nitrile complexes. [ 29,32,58–63 ] The average Ru–Cl bonds in the cationic part [RuCl(N≡CR) 5 ] + ( 4a , R = Me; 4b , R = Ph) are with 2.3789(8) and 2.3863(18) Å longer than in [RuCl 4 (N≡CR) 2 ] – [ 4a : 2.3528(8) Å, 4b : 2.3539(17) Å], which is attributed to the chloride being in trans position to an acetonitrile ligand. [ [29, 32,58 ] The respective N–Ru–N, N–Ru–Cl, Cl–Ru–Cl, Ru–N–C and N–C–C bond angles are in accordance with literature values (Table 2).…”

“…Crystallographic data and details of the data collection and structure determination for 3, 4a,b and 6. [29,32,[58][59][60][61][62][63] The average Ru-Cl bonds in the cationic part [RuCl(NϵCR) 5 ] + (4a, R = Me; 4b, R = Ph) are with 17Å], which is attributed to the chloride being in trans position to an acetonitrile ligand. [[29, 32,58] The respective N-Ru-N, N-Ru-Cl, Cl-Ru-Cl, Ru-N-C and N-C-C bond angles are in accordance with literature values (Table 2).…”

“…[[29, 32,58] The respective N-Ru-N, N-Ru-Cl, Cl-Ru-Cl, Ru-N-C and N-C-C bond angles are in accordance with literature values (Table 2). [29,32,[58][59][60][61][62][63] One of the benzonitrile ligands (nitrile associated with N5) of [RuCl(NϵCPh) 5 ] + is disordered and has been refined to split occupancies of 0.673/ 0.327 ( Figure 2), resulting in bond angles of 155.2(9)°(Ru1-N5-C29') and 153.5(18)°(Ru1-N5-C29) with the bent nature of the benzonitrile ligand at an angle of 167(3)°( N5-C29-C30) and 176.6(3)°(N5-C29'-C30'), respec-ARTICLE Table 2. Selected bond parameters /Å/°of 4a,b.…”