Treatment of [Ir(dtbpy)Cl₃(DMF)] (DMF = N,N-dimethylformamide; dtbpy = 4,4'-di-tert-2,2'-dipyridyl) with Me₃SiCH₂MgCl afforded the Ir(IIl) silyl complex [Ir(dtbpy)(SiMe₃)Me(CH₂SiMe₃)], which reacted with t-BuNC and PhC≡CH to give [Ir(dtbpy)(SiMe₃)Me(CH₂SiMe₃)(t-BuNC)] and [Ir(dtbpy)(SiMe₃)(C≡CPh)(μ-C≡CPh)]₂, respectively. Treatment of [Ir(dtbpy)Cl₃(DMF)] with PhMe₂CCH₂MgCl afforded cyclometalated [Ir(dtbpy)(C₆H₄CMe₃-2)(CH₂CMe₂C₆H₄)] that exhibits an Ir-HC agostic interaction between the Ir center and a tert-butyl C-H group. Treatment of [Ir(dtbpy)(C₆H₄CMe₃-2)(CH₂CMe₂C₆H₄)] with NOBF₄, tetracyanoethylene and pyridinium tribromide afforded [Ir(dtbpy)(C₆H₃CMe₃-2-NO₂-4)(CH₂CMe₂C₆H₃NO₂-4], [Ir(dtbpy)(C₆H₄CMe₃-2)(CH₂CMe₂C₆H₃{C₂(CN)₃}-4)] and [Ir(dtbpy)(C₆H₄CMe₃-2)(CH₂CMe₂C₆H₃Br-4)]. Treatment...[ Read more ]

Treatment of [Ir(dtbpy)Cl₃(DMF)] (DMF = N,N-dimethylformamide; dtbpy = 4,4'-di-tert-2,2'-dipyridyl) with Me₃SiCH₂MgCl afforded the Ir(IIl) silyl complex [Ir(dtbpy)(SiMe₃)Me(CH₂SiMe₃)], which reacted with t-BuNC and PhC≡CH to give [Ir(dtbpy)(SiMe₃)Me(CH₂SiMe₃)(t-BuNC)] and [Ir(dtbpy)(SiMe₃)(C≡CPh)(μ-C≡CPh)]₂, respectively. Treatment of [Ir(dtbpy)Cl₃(DMF)] with PhMe₂CCH₂MgCl afforded cyclometalated [Ir(dtbpy)(C₆H₄CMe₃-2)(CH₂CMe₂C₆H₄)] that exhibits an Ir-HC agostic interaction between the Ir center and a tert-butyl C-H group. Treatment of [Ir(dtbpy)(C₆H₄CMe₃-2)(CH₂CMe₂C₆H₄)] with NOBF₄, tetracyanoethylene and pyridinium tribromide afforded [Ir(dtbpy)(C₆H₃CMe₃-2-NO₂-4)(CH₂CMe₂C₆H₃NO₂-4], [Ir(dtbpy)(C₆H₄CMe₃-2)(CH₂CMe₂C₆H₃{C₂(CN)₃}-4)] and [Ir(dtbpy)(C₆H₄CMe₃-2)(CH₂CMe₂C₆H₃Br-4)]. Treatment of [Ir(dtbpy)(C₆H₄CMe₃-2)(CH₂CMe₂C₆H₄)] with diethyl meleate led to isolation of the iridafuran [Ir(dtbpy){k²(C,O)-C(CO₂Et)=CHC(OEt)=O} (CH₂CMe₂C₆H₄)].

Oxidation of [Ir(dtbpy)(CH₂CMe₂C₆H₄)( μ-tolS)]₂ and [Ir(dtbpy)(CH₂CMe₂Ph)(tdt)] (tdt = toluene-3,4-dithiolato) afforded the mixed-valence Ir(IIl)-Ir(lV) [Ir(dtbpy)(CH₂CMe₂C₆H₄)(μ-tolS)]₂[BF₄] and the Ir(lV)-Ir(lV) [Ir(dtbpy)(CH₂CMe₂Ph)(tdt)][BF₄]₂ compounds, respectively.

Treatment of [Ir(dtbpy)Cl₃(DMF)] with (p-xyl)MgBr (xyl = dimethylphenyl) afforded the Ir(IIl) tri-aryl complex [Ir(dtbpy)(p-xyl)₃]. Oxidation of [Ir(dtbpy)(p-xyl)₃] with AgOTf in THF afforded the ID polymer [Ir(dtbpy)(p-xyl)₃(AgOTf)₃]_n. Alkylation of [Ir(dtbpy)Cl₃(DMF)] with Ar_fMgBr (Ar_f = 3,5-bis(trifluoromethyl)phenyl) afforded [Ir(dtbpy)(Ar_f)(DMF)(Cl_0.7Br_0.3)₂] that reacted with o-xylNC to give [Ir(dtbpy)(Ar_f)(o-xylNC)(Cl_0.7Br_0.3)₂].

[Cp*Ir(III)(ppy)(H₂O)]⁺ (Hppy = 2-phenylpyridine) can catalyze oxidation and aziridination of styrene with PhIO and PhINTs (Ts = tosyl), respectively. Treatment of [Cp*Ir(III)(ppy)(NCMe)]⁺ with PhI=NTs led to insertion of the NTs group into the Ir-C(ppy) bond and the formation of [Cp*Ir(III)(TsN-ppy)(NCMe)]⁺. Treatment of [Cp*Ir(III)(ppy)(NCMe)]⁺ with phenylacetylene, 3-butyn-1-o1 and 2-phenyl-but-3-yn-2-o1 led to migratory insertion of the vinylidene and allenyldiene into the Ir-C(ppy) bond and the formation of [Cp*Ir{(Ph)(H)C-η³-CC(Ph)C(H)-ppy}]⁺, [Cp*Ir{η³-H₂CC(H)C-C(H)-ppy}]⁺ and [Cp*Ir{(C₆H₄)(H₂C)C-η²-C(H)C(H)-ppy}] ⁺, respectively. Treatment of [Cp*Ir(III)(ppy)(H₂O)]⁺ with RE-ER afforded the adducts [Cp*Ir(ppy)(η¹-RE-ER)]⁺(E = S, Se and Te, R = tol and Ph), which reacted with Ag(OTf) gave [Cp*Ir(RE-ppy)(H₂O)]²⁺.

Treatment of (Sp)-^tBuPhP(O)H (HL¹) with PdCl₂(MeCN)₂ afforded [Pd{(L¹)₂H}]₂(μ-Cl)₂. X-ray crystallography established that HL¹ binds to Pd(ll) with the retention of configuration at phosphorus. Treatment of [Pd{(L¹)₂H}]₂(μ-Cl)₂ with Na[S₂CNEt₂] gave Pd[(L¹)₂H](S₂CNEt₂), which reacted with V(O)(acac)₂ (acac = acetylacetone) and Cu(NO₃)₂ to give V(O)[Pd(L¹)₂(S₂CNEt₂)]₂ and Cu[Pd(L¹)₂(S₂CNEt₂)]₂, respectively.

Chiral tetradentate sulfoxide-containing Schiff base ligands, N,N'-bis[2-(S)-(p-tolylsulfinyl)benzylidene]ethylenediamine (L²),(1R,2R)-N,N'-bis[2-(S)-(p-tolylsulfinyl)benzylidene]-1,2-cyclohexanedimine ((R,R)-L³), and (1S,2S)-N,N'-bis[2-(S)-(p-tolylsulfinyl)benzylidene]-1,2-cyclohexanedimine ((S,S)-L³) have been synthesized. Treatment of [Ru(PPh₃)₃Cl₂] with L afforded trans-[Ru(L)Cl₂] (L = L², (R,R)-L³ and (S,S)-L³), respectively. The configuration and S-bonding mode of the tetradentate sulfoxide ligands in these complexes have been unambiguously established by X-ray crystallography. Tridentate N, N-bis[2-(S)-(p-tolylsulfinyl)benzyl]methylamine (L⁴) and 1,5-bis[(S)-(p-tolylsulfinyl)methyl]benzene (L⁵) have been synthesized. Treatment of [Pd(NCMe)₄]²⁺ with L⁴ afforded [Pd(L⁴)(NCMe)]²⁺.