Metal–Ligand Cooperative C–H Bond Formation by Cyclopentadienone Platinum Complexes

Thermodynamic data are reported for the addition of pyridine and bipyridine in benzene solution to monothio-β-diketone complexes, ML2, of nickel(11), copper(11), zinc(11) and mercury(11). NiL2 gives NiL2(py)2 and NiL(bpy); ZnL2 gives ZnL2(py) and ZnL2(bpy); in both cases the data show that bipyridine is bidentate. CuL2 gives CuL2 (py) and CuL2 (bpy), with almost equal enthalpies of formation, but the higher stability of CuL2(bpy) shows bipyridine is probably bidentate. HgL2 gives HgL2(py) and a reaction with bipyridine which shows that an extremely unstable adduct is formed. All data were obtained by calorimetric titration.

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Thermodynamics of metal-ligand bond formation

Journal of Organometallic Chemistry ◽

10.1016/s0022-328x(00)92509-9 ◽

1977 ◽

Vol 132 (1) ◽

pp. 1-7 ◽

Cited By ~ 13

Author(s):

D.P. Graddon ◽

J. Mondal

Keyword(s):

Bond Formation ◽

Metal Ligand ◽

Ligand Bond

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Rh(I) Complex with a Tridentate Pyridine–Amino–Olefin Actor Ligand–Metal–Ligand Cooperative Activation of CO2 and Phenylisocyanate under C–C and Rh–E (E = O, N) Bond Formation

Organometallics ◽

10.1021/acs.organomet.9b00094 ◽

2019 ◽

Vol 38 (8) ◽

pp. 1787-1799 ◽

Cited By ~ 3

Author(s):

Isabell Heuermann ◽

Benjamin Heitmann ◽

Rasmus Stichauer ◽

Daniel Duvinage ◽

Matthias Vogt

Keyword(s):

Bond Formation ◽

Cooperative Activation ◽

Metal Ligand

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Thermodynamics of metalligand bond formation

Journal of Organometallic Chemistry ◽

10.1016/0022-328x(86)80518-6 ◽

1986 ◽

Vol 317 (2) ◽

pp. 153-157 ◽

Cited By ~ 5

Author(s):

Y. Farhangi ◽

D.P. Graddon

Keyword(s):

Bond Formation ◽

Metal Ligand ◽

Ligand Bond

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Thermodynamics of metal-ligand bond formation. II. Zinc, cadmium, and mercury(II) complexes of o,o-dialkyldithiophosphates

Australian Journal of Chemistry ◽

10.1071/ch9712077 ◽

1971 ◽

Vol 24 (10) ◽

pp. 2077 ◽

Cited By ~ 9

Author(s):

DR Dakternieks ◽

DP Graddon

Keyword(s):

Metal Atom ◽

Alkyl Group ◽

Thermodynamic Data ◽

Benzene Solution ◽

Bond Formation ◽

Free Energies ◽

Zinc Cadmium ◽

Metal Ligand ◽

Ligand Bond

The reactions of 0,O-dialkyldithiophosphato complexes, {(R0)2PSz}zM (M = Zn, Cd, Hg), to form dimers and 1 : 1 and 1 : 2 adducts with pyridine have been studied calorimetrically in benzene solution a t 30�C. While variation of the alkyl group has little effect, variation of the metal atom causes marked changes in both free energies and enthalpies of reaction. Average values of thermodynamic data obtained are as follows (AGOao3 and AH0300 in k J mol-l, AS0a03 in J K-l mol-l) :

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Thermodynamics of metal-ligand bond formation. XXV. Addition of bases to Bis[O,O'-diethyl thiomalonato]nickel(II) in various solvents

Australian Journal of Chemistry ◽

10.1071/ch9770495 ◽

1977 ◽

Vol 30 (3) ◽

pp. 495 ◽

Cited By ~ 2

Author(s):

L Ang ◽

DP Graddon ◽

VAK Ng

Keyword(s):

Thermodynamic Data ◽

Driving Force ◽

Bond Formation ◽

Adduct Formation ◽

Calorimetric Measurements ◽

Carbon Tetra ◽

Metal Ligand ◽

Ligand Bond

Thermodynamic data have been obtained from spectroscopic and calorimetric measurements for the addition of pyridine and 4- methylpyridine to bis(O,O?-diethyl thiomalonato)nickel(II), Ni(etm)2, in solution in cyclohexane, benzene, 1,2-dichloroethane, acetonitrile, butan-2-one and carbon tetra-chloride. In each solvent two base molecules add successively, giving Ni(etm)2B then Ni(etm)2B2. There are only small variations in K1 and K2 in different solvents; typically K1 ≈ 200, K2 ≈ 100 l. mol-1, ΔH�1+2 ≈ -65, ΔH�2 ≈ 0 kJ mol-1 at 30�C, but in benzene and cyclohexane ΔH�2 ≈ -25 and in cyclohexane ΔH�1+2 ≈ -100 kJ mol-1. The main driving force for adduct formation is apparently the formation of the first Ni-N bond, which is accompanied by a spin change.

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