Treatment of [Ir(dtbpy)Cl
3(DMF)] (DMF = N,N-dimethylformamide; dtbpy = 4,4'-di-tert-2,2'-dipyridyl) with Me
3SiCH
2MgCl afforded the Ir(IIl) silyl complex [Ir(dtbpy)(SiMe
3)Me(CH
2SiMe
3)], which reacted with t-BuNC and PhC≡CH to give [Ir(dtbpy)(SiMe
3)Me(CH
2SiMe
3)(t-BuNC)] and [Ir(dtbpy)(SiMe
3)(C≡CPh)(μ-C≡CPh)]
2, respectively. Treatment of [Ir(dtbpy)Cl
3(DMF)] with PhMe
2CCH
2MgCl afforded cyclometalated [Ir(dtbpy)(C
6H
4CMe
3-2)(CH
2CMe
2C
6H
4)] that exhibits an Ir-HC agostic interaction between the Ir center and a tert-butyl C-H group. Treatment of [Ir(dtbpy)(C
6H
4CMe
3-2)(CH
2CMe
2C
6H
4)] with NOBF
4, tetracyanoethylene and pyridinium tribromide afforded [Ir(dtbpy)(C
6H
3CMe
3-2-NO
2-4)(CH
2CMe
2C
6H
3NO
2-4], [Ir(dtbpy)(C
6H
4CMe
3-2)(CH
2CMe
2C
6H
3{C
2(CN)
3}-4)] and [Ir(dtbpy)(C
6H
4CMe
3-2)(CH
2CMe
2C
6H
3Br-4)]. Treatment...[
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Treatment of [Ir(dtbpy)Cl
3(DMF)] (DMF = N,N-dimethylformamide; dtbpy = 4,4'-di-tert-2,2'-dipyridyl) with Me
3SiCH
2MgCl afforded the Ir(IIl) silyl complex [Ir(dtbpy)(SiMe
3)Me(CH
2SiMe
3)], which reacted with t-BuNC and PhC≡CH to give [Ir(dtbpy)(SiMe
3)Me(CH
2SiMe
3)(t-BuNC)] and [Ir(dtbpy)(SiMe
3)(C≡CPh)(μ-C≡CPh)]
2, respectively. Treatment of [Ir(dtbpy)Cl
3(DMF)] with PhMe
2CCH
2MgCl afforded cyclometalated [Ir(dtbpy)(C
6H
4CMe
3-2)(CH
2CMe
2C
6H
4)] that exhibits an Ir-HC agostic interaction between the Ir center and a tert-butyl C-H group. Treatment of [Ir(dtbpy)(C
6H
4CMe
3-2)(CH
2CMe
2C
6H
4)] with NOBF
4, tetracyanoethylene and pyridinium tribromide afforded [Ir(dtbpy)(C
6H
3CMe
3-2-NO
2-4)(CH
2CMe
2C
6H
3NO
2-4], [Ir(dtbpy)(C
6H
4CMe
3-2)(CH
2CMe
2C
6H
3{C
2(CN)
3}-4)] and [Ir(dtbpy)(C
6H
4CMe
3-2)(CH
2CMe
2C
6H
3Br-4)]. Treatment of [Ir(dtbpy)(C
6H
4CMe
3-2)(CH
2CMe
2C
6H
4)] with diethyl meleate led to isolation of the iridafuran [Ir(dtbpy){k
2(C,O)-C(CO
2Et)=CHC(OEt)=O} (CH
2CMe
2C
6H
4)].
Oxidation of [Ir(dtbpy)(CH
2CMe
2C
6H
4)( μ-tolS)]
2 and [Ir(dtbpy)(CH
2CMe
2Ph)(tdt)] (tdt = toluene-3,4-dithiolato) afforded the mixed-valence Ir(IIl)-Ir(lV) [Ir(dtbpy)(CH
2CMe
2C
6H
4)(μ-tolS)]
2[BF
4] and the Ir(lV)-Ir(lV) [Ir(dtbpy)(CH
2CMe
2Ph)(tdt)][BF
4]
2 compounds, respectively.
Treatment of [Ir(dtbpy)Cl
3(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)Cl
3(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)(H
2O)]
+ (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-η
3-CC(Ph)C(H)-ppy}]
+, [Cp*Ir{η
3-H
2CC(H)C-C(H)-ppy}]
+ and [Cp*Ir{(C
6H
4)(H
2C)C-η
2-C(H)C(H)-ppy}]
+, respectively. Treatment of [Cp*Ir(III)(ppy)(H
2O)]
+ with RE-ER afforded the adducts [Cp*Ir(ppy)(η
1-RE-ER)]
+(E = S, Se and Te, R = tol and Ph), which reacted with Ag(OTf) gave [Cp*Ir(RE-ppy)(H
2O)]
2+.
Treatment of (Sp)-
tBuPhP(O)H (HL
1) with PdCl
2(MeCN)
2 afforded [Pd{(L
1)
2H}]
2(μ-Cl)
2. X-ray crystallography established that HL
1 binds to Pd(ll) with the retention of configuration at phosphorus. Treatment of [Pd{(L
1)
2H}]
2(μ-Cl)
2 with Na[S
2CNEt
2] gave Pd[(L
1)
2H](S
2CNEt
2), which reacted with V(O)(acac)
2 (acac = acetylacetone) and Cu(NO
3)
2 to give V(O)[Pd(L
1)
2(S
2CNEt
2)]
2 and Cu[Pd(L
1)
2(S
2CNEt
2)]
2, respectively.
Chiral tetradentate sulfoxide-containing Schiff base ligands, N,N'-bis[2-(S)-(p-tolylsulfinyl)benzylidene]ethylenediamine (L
2),(1R,2R)-N,N'-bis[2-(S)-(p-tolylsulfinyl)benzylidene]-1,2-cyclohexanedimine ((R,R)-L
3), and (1S,2S)-N,N'-bis[2-(S)-(p-tolylsulfinyl)benzylidene]-1,2-cyclohexanedimine ((S,S)-L
3) have been synthesized. Treatment of [Ru(PPh
3)
3Cl
2] with L afforded trans-[Ru(L)Cl
2] (L = L
2, (R,R)-L
3 and (S,S)-L
3), 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 (L
4) and 1,5-bis[(S)-(p-tolylsulfinyl)methyl]benzene (L
5) have been synthesized. Treatment of [Pd(NCMe)
4]
2+ with L
4 afforded [Pd(L
4)(NCMe)]
2+.
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