Top Organomet Chem (2016) 59: 59–102
DOI: 10.1007/3418_2015_162
# Springer International Publishing Switzerland 2015
Published online: 23 December 2015
Reactivity and Catalysis at Sites Trans to the
[Ru–Ru] Bond
Indranil Dutta, Gargi Sengupta, and Jitendra K. Bera
Abstract The reactivity and catalysis at axial sites of [Ru–Ru] bonded compounds
are described. Effect of axial donor at axial site of a [Ru–Ru] single bond, having
electronic configuration σ
2
π
4
δ
2
δ*
2
π*
4 , is examined. It is shown that the stronger
donor leads to longer metal–metal distances. The C–H bond activation and C–C
bond formation are studied at axial site of a [Ru 2 (CO) 4 ]
2+ core. Metal–metal and
metal–ligand cooperation is exploited for catalytic alcohol dehydrogenation to
aldehyde and subsequent coupling with amine to access imine selectively. Catalytic
carbene transfer reactions are discussed for a wide range of diruthenium(I,I)
compounds. Catalytic utility of metal–metal multiply bonded diruthenium(II,III)
compounds for C–H amination reaction is also discussed.
Keywords Acceptorless alcohol dehydrogenation • Allylic C–H activation • Axial
reactivity • Carbenoid C–H insertion • C–H activation • Cycloprpanation •
Diruthenium compounds • Metal nitride • Metal–ligand cooperation • Metal–
metal bond
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
2 Diruthenium(I,I) Complexes Bearing Paddlewheel [Ru 2 (CO) 4 ]
2+ Core . . . . . . . . . . . . . . . . . . 61
3 Effect of Axial Donor on the [Ru–Ru] Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
4 C–H Bond Activation at Axial Site of a [Ru
I
–Ru
I
] Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
5 C–C Bond Formation at Axial Site of a [Ru
I
–Ru
I
] Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
6 Alcohol Dehydrogenation at Axial Site of a [Ru
I
–Ru
I ] Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
7 Cyclopropanation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
8 Carbenoid C–H Insertion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
9 Vinylogous Reactivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
I. Dutta, G. Sengupta, and J.K. Bera (*)
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India
e-mail: jbera@iitk.ac.in
DOI: 10.1007/3418_2015_162
# Springer International Publishing Switzerland 2015
Published online: 23 December 2015
Reactivity and Catalysis at Sites Trans to the
[Ru–Ru] Bond
Indranil Dutta, Gargi Sengupta, and Jitendra K. Bera
Abstract The reactivity and catalysis at axial sites of [Ru–Ru] bonded compounds
are described. Effect of axial donor at axial site of a [Ru–Ru] single bond, having
electronic configuration σ
2
π
4
δ
2
δ*
2
π*
4 , is examined. It is shown that the stronger
donor leads to longer metal–metal distances. The C–H bond activation and C–C
bond formation are studied at axial site of a [Ru 2 (CO) 4 ]
2+ core. Metal–metal and
metal–ligand cooperation is exploited for catalytic alcohol dehydrogenation to
aldehyde and subsequent coupling with amine to access imine selectively. Catalytic
carbene transfer reactions are discussed for a wide range of diruthenium(I,I)
compounds. Catalytic utility of metal–metal multiply bonded diruthenium(II,III)
compounds for C–H amination reaction is also discussed.
Keywords Acceptorless alcohol dehydrogenation • Allylic C–H activation • Axial
reactivity • Carbenoid C–H insertion • C–H activation • Cycloprpanation •
Diruthenium compounds • Metal nitride • Metal–ligand cooperation • Metal–
metal bond
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
2 Diruthenium(I,I) Complexes Bearing Paddlewheel [Ru 2 (CO) 4 ]
2+ Core . . . . . . . . . . . . . . . . . . 61
3 Effect of Axial Donor on the [Ru–Ru] Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
4 C–H Bond Activation at Axial Site of a [Ru
I
–Ru
I
] Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
5 C–C Bond Formation at Axial Site of a [Ru
I
–Ru
I
] Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
6 Alcohol Dehydrogenation at Axial Site of a [Ru
I
–Ru
I ] Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
7 Cyclopropanation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
8 Carbenoid C–H Insertion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
9 Vinylogous Reactivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
I. Dutta, G. Sengupta, and J.K. Bera (*)
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India
e-mail: jbera@iitk.ac.in