Synthesis, Structures, and Reactivity of Single and Double Cyclometalated Complexes Formed by Reactions of [Cp*MCl₂]₂ (M = Ir and Rh) with Dinaphthyl Phosphines

Abstract

Reactions of two dinaphthyl phosphines with [Cp*IrCl 2 ] 2 have been carried out. In the case of di(α-naphthyl)phenylphosphine ( 1a ), a simple P-coordinated neutral adduct 2a is obtained. However, tert -butyldi(α-naphthyl)phenylphosphine ( 1b ) is cyclometalated to form [Cp*IrCl(P^C)] ( 3b ). Complexes 2a and 3a undergo further cyclometalation to give the corresponding double cyclometalated complexes [Cp*Ir(C^P^C)] ( 4a , b ) upon heating. In the presence of sodium acetate, reactions of 1a , b with [Cp*IrCl 2 ] 2 directly afford the final double cyclometalated complexes ( 4a , b ). In the absence of acetate, [Cp*RhCl 2 ] 2 shows no reaction with 1a , b , whereas with acetate the reactions form the corresponding single cyclometalated complexes [Cp*RhCl(P^C)] ( 5a , b ), which react with t BuOK to form the corresponding rhodium hydride complexes ( 6a , b ). Treatment of 4a with CuCl 2 or I 2 leads to opening of two Ir–C σ bonds to yield the corresponding P-coordinated iridium dihalide ( 7 or 8 ) by means of an intramolecular C–C coupling reaction. A new chiral phosphine ( 11 ) is formed by the ligand-exchange reaction of 8 with PMe 3 . Reactions of the single cycloiridated complex 3b with terminal aromatic alkynes result in the corresponding five- and six-membered doubly cycloiridated complex 12 and/or η 2 -alkene coordinated complexes 13–15 ; the latter discloses that the electronic effect of terminal alkynes affects the regioselectivity. While the single cyclorhodated complex 5b reacts with terminal aromatic alkynes to form the corresponding six-membered cyclometalated complexes 16a–c by vinylidene rearrangement/1,1-insertion. Plausible pathways for formation of insertion products 13–16 were proposed. Molecular structures of twelve new complexes were determined by X-ray diffraction.

Transmetallation of Bis(6‐diphenylphosphinoacenaphth‐5‐yl)‐Mercury and ‐Tributyltin with Precious Metal Chlorides

“…At present, there is great interest in peri-substituted 8-diorganophosphinonaphth-1-yl and 6-diorganophosphinoacenaphth-5-yl precious metal compounds of Re, [1] Ru, [2,3] Ir, [4] Rh, [5] and particularly, Au, [6][7][8][9][10][11][12][13][14][15][16] which involves the synthesis, bonding analysis and applications in bond activation and catalysis. Often, the synthesis of these compounds entails the oxidative addition of the metal to a C-H [1][2][3][4][5] or C-X (X = halide) bond in peri-position to a structurally directing P atom that takes part in coordination to the precious metal.…”

“…At present, there is great interest in peri-substituted 8-diorganophosphinonaphth-1-yl and 6-diorganophosphinoacenaphth-5-yl precious metal compounds of Re, [1] Ru, [2,3] Ir, [4] Rh, [5] and particularly, Au, [6][7][8][9][10][11][12][13][14][15][16] which involves the synthesis, bonding analysis and applications in bond activation and catalysis. Often, the synthesis of these compounds entails the oxidative addition of the metal to a C-H [1][2][3][4][5] or C-X (X = halide) bond in peri-position to a structurally directing P atom that takes part in coordination to the precious metal. [6][7][8][9][10][11][12][13][14] Recently, we have used the well-defined 5-diorganophosphinoacenaphth-6-yllithium, RLi (1, R = 5-Ph 2 P-Ace-6-), [17] as starting material for the synthesis of two related transmetallation reagents R 2 Hg (2, R = 6-Ph 2 P-Ace-5-) [15] and RSnBu 3 (3, R = 6-Ph 2 P-Ace-5-), [18] which offer the advantage to be nonreductive and bench stable (Scheme 1).…”

“…[19] The reaction of mercury reagent 2 with (tht)AuCl gave rise to the formation of the complex R 2 Hg•AuCl (4), in which the two transition ARTICLE metals are in close proximity and engage in Au•••Hg metallophilic interaction (Scheme 1). During the course of a few days, 4 converts in the cationic gold(III) complex cis-[R 2 Au][Cl] (5), whereby elemental Hg was expelled (Scheme 1). [15] The transmetallation reaction of the tin reagent 3 with (tht)AuCl 3 provided the cationic gold(III) complex trans-[R 2 Au][Cl] (6), the structural isomer of 5 (Scheme 1).…”

Mixing Polyaromatic Scaffolds and Main Group Elements: Synthesis, Coordination and Optical Properties of Naphthyl‐Fused Heteropines

“…HSiCl 3 (270 mg, 2.0 mmol, 10 eq) is added dropwise and then heated to reflux 1 h. The mixture is filtered on alumina under argon and wash with distillated THF. The solvent is evaporated under the schlenk line vacuum and the resulting intermediate 8 [9a] is dissolved in 10 mL of dry DCM, then MeOTf (98 mg, 0.6 mmol, 3 eq) is added to 0 °C. The mixture is stirred at R.T. for 1 h30 and finally washed with an extraction H 2 O/DCM.…”

Isomerization of a cationic (η5-C5Me5)Ir(III) complex involving remote C–C and C–H bond formation

“…Perhaps the best-known example of phosphine non-innocent behavior is their facile cyclometalation upon coordination to late transition metals [4]. More recently, startling examples describing the nickel-and palladium-mediated dearomatization of dialkylbiaryl phosphines have been reported (Fig.…”