Oxidation of a series of Ru(Et
2dtc)
2L
2 (L=labile group) complexes were studied. Treatment of cis-Ru(Et
2dtc)
2(dmso)
2 with I
2 led to isolation of trimeric [Ru
3(Et
2dtc)
6(dmso)
2](I
3)
2, presumably via self-assembly. Reactions of Ru(Et
2dtc)(PPh
3)
2(CO)(OTf) with N
2H
4[black circle]xH
2O and NH
2OH gave the structurally characterized Ru(Et
2dtc)(PPh
3)
2(CO)(H
2NNH
2)(OTf) and Ru(Et
2dtc)(PPh
3)
2(CO)(NH
2OH)(OTf), respectively.
2 2 3 3 2 2 2 2 2 2 3 2 2 2 3 2 2 2 3 2...[
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Oxidation of a series of Ru(Et
2dtc)
2L
2 (L=labile group) complexes were studied. Treatment of cis-Ru(Et
2dtc)
2(dmso)
2 with I
2 led to isolation of trimeric [Ru
3(Et
2dtc)
6(dmso)
2](I
3)
2, presumably via self-assembly. Reactions of Ru(Et
2dtc)(PPh
3)
2(CO)(OTf) with N
2H
4[black circle]xH
2O and NH
2OH gave the structurally characterized Ru(Et
2dtc)(PPh
3)
2(CO)(H
2NNH
2)(OTf) and Ru(Et
2dtc)(PPh
3)
2(CO)(NH
2OH)(OTf), respectively.
A series of Ru complexes with bis(dialkylphosphornyl)imide [N(PR
2S)
2] (R=Ph, i-Pr) ligands were synthesized. Treatment of Ru(PPh
3)
3CI
2 with K[N(PR
2S)
2] gave structurally characterized Ru[N(PR
2S)
2]
2(PPh
3) (R=Ph, i-Pr). Ru[N(PPh
2S)
2]
2(PPh
3) was found to catalyze hydrogenation of styrene to ethylbenzene. In addition, Ru[N(PPh
2S)
2]
2(PPh
3) reacted with both π acids (e.g. SO
2, t-Bupy) and Lewis bases (e.g. NH
3) to form a series of adducts. Novel Ru(II) diazene cis-Ru[N(PPh
2)
2]
2(PPh
3)(NH=NH) and sulfur monoxide cis-Ru[N(PPh
2S)
2]
2(PPh
3)(SO) complexes were isolated and structurally characterized. Stable nitrido and oxo-Os(VI) complexes trapls-Os(N)[N(PR
2S)
2]
2Cl and trans-Os[N(PR
2S)
2]
2O
2(R=Ph, i-Pr) were also synthesized and structurally characterized.
Acylimido-Re(V) species trans-Re(NCOCF
3)[N(PPh
2S)
2]
2(OCOCF
3) and tracts-Re(NCOCHCl
2)[N(PPh
2S)
2]
2Cl can be isolated by acylation of Re(N)[N(PPh
2S)
2]
2. Hydrolysis of acylimido-Re(V) [RCON=Re] gave Re=NH (for R=CF
3, CCl
3) and Re=O (for R=CH
2Cl, CHCl
2 and CH
3) species, depending on the nature of R groups.
A series of heterobimetallic nitrido-bridged complexes with a trioxo-Os(VIII) moiety were synthesized by metathesis reaction between [n-Bu
4N][OsO
3N] and [ML
n][OTf] and were characterized by X-ray crystallography. Based on the structurally data, it was found that the nature of M-N-OS linkage depends on the electronic configuration of M. For d[to the power of 10]-d[to the power of 8]-configurated M (M=Au(I), Pt(II) and Ir(I)), the bonding is donor-acceptor type [M[back arrow]N[is equivalent to]Os]. For (NO)(por)Ru(NOsO
3), the bonding can be described as [Os=N-Ru].
Reactions of [OsN(TolS
2)
2] with a series of organometallic electrophiles were studied. [Au(PPh
3)]
+ was found to attack the more basic sulfur while sterically bulky [Ir(PPh
3)
2(CO)]
+ add to the less hindered nitride to yield (TolS
2)OsN[STolSAu(PPh
3)] and (PPh
3)
2(CO)IrNOs(TolS
2)
2, respectively.
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