Treatment of Ru(H)Cl(CO)(PPh
3)
3 and Ru(H)Cl(CO)(PCy
3)
2 (Cy = cyclohexyl) with NaL
OEt (L
OEt- = [(η
5-C
5H
5)Co{P(O)(OEt)
2}
3]
-) afforded L
OEt(CO)(PR
3)RuH (R = Ph (1) and Cy (2)), which have been characterized by X-ray crystallography. It was found that the use of recrystallized samples of the Ru hydridesas starting materials and removal of the phosphines from the crude products with hexane are critical for the synthesis of complexes 1 and 2 in pure form. The protonation of 1 with HBF
4 in CD
2Cl
2 at low temperature resulted in appearance of new
1H NMR signals at δ 11.78, -12.52 and -17.61 ppm, which can be assigned to Ru hydride species. The protonation of 1 with HCl in Et
2O afforded L
OEt(CO)(PR
3)RuCl. The reactions between 1 and RSO
2N
3 yielded the (arylsulfonyl)amido complexes L
OEt(CO)(PPh
3)R...[
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Treatment of Ru(H)Cl(CO)(PPh
3)
3 and Ru(H)Cl(CO)(PCy
3)
2 (Cy = cyclohexyl) with NaL
OEt (L
OEt- = [(η
5-C
5H
5)Co{P(O)(OEt)
2}
3]
-) afforded L
OEt(CO)(PR
3)RuH (R = Ph (1) and Cy (2)), which have been characterized by X-ray crystallography. It was found that the use of recrystallized samples of the Ru hydridesas starting materials and removal of the phosphines from the crude products with hexane are critical for the synthesis of complexes 1 and 2 in pure form. The protonation of 1 with HBF
4 in CD
2Cl
2 at low temperature resulted in appearance of new
1H NMR signals at δ 11.78, -12.52 and -17.61 ppm, which can be assigned to Ru hydride species. The protonation of 1 with HCl in Et
2O afforded L
OEt(CO)(PR
3)RuCl. The reactions between 1 and RSO
2N
3 yielded the (arylsulfonyl)amido complexes L
OEt(CO)(PPh
3)Ru(NHSO
2R) (R = 2,4,6-i-Pr
3C
6H
3 (3), 4-t-BuC
6H
4 (4), 4-MeC
6H
4 (5)). The crystal structure of 3 has been determined. The photolysis of 5 resulted in the complex L
OEt(MeCN)(PPh
3)Ru(NHSO
2C
6H
4Me-4). Treatment of Ru(PCy
3)
2(Cl)
2(=CHPh) with NaL
OEt afforded L
OEtRu(PCy
3)(Cl)(=CHPh) which can catalyze the ring-closing metathesis of diethyl 1,2-diallylmalonate. The reaction between (Et
4N)
2MoS
4 and NaL
OEt yielded the dinuclear Mo(V) sulfido complex [L
OEtMo(O)(μ-S)]
2 characterized by X-ray crystallography.
Four functionalized N^C ligands, 3-(pyridin-2-yl)phenol (HL1), diethyl hydroxy(4-(pyridin-2-yl)phenyl)ethylphosphonate (HL2), 2-(thiophen-3-yl)pyridine (HL3), and hydroxy(4-(pyridin-2-yl)phenyl)methylphosphonic acid (HL4), have been synthesized. Refluxing IrCl
3 with HL1 in methoxyethanol/H
2O gives [Ir(L1)
2Cl]
2. Treatment of [Ir(L1)
2Cl]
2 with 3 equivalents of silver triflate (AgOTf) yielded [Ir(L1)
2(dtbpy){Ag(MeCN)
2}](OTf)
2. The crystal structure of [Ir(L1)
2(dtbpy){Ag(MeCN)
2}](OTf)
2 shows that there is an interaction between the [Ag(MeCN)
2]
+ moiety and the ipso carbons of the two L1 ligands. Reaction of [Ir(η
5-C
5Me
5)Cl
2]
2 with HL2 in the presence of NaOAc resulted in the formation of Ir(η
5-C
5Me
5)(L2)Cl. Reaction between LiL3 and [Ir(COD)Cl]
2 yielded [Ir(COD)(L3)] (COD = 1,4-cyclooctadiene) that underwent oxidative addition with MeI to give [Ir(COD)(L3)(CH
3)(I)]. The reaction between [Ru(η
6-p-cymene)Cl
2]
2 and HL2 in the presence of NaOAc yielded Ru(η
6-p-cymene)(L2)(Cl).
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