Stoichiometric CH Bond Cleavage Reaction in a Bis(carboxylato)ruthenium(II) Complex and Its Application to the Catalytic H-D Exchange Reaction of Carboxylic Acids
is indispensable for the CH bondcleavagereaction. Complex 1 a establishes an equilibrium with 2 a (or 5 a) in solution. In this reaction, one coordinated carboxylato ligand is engaged in the CH bondcleavagereaction as a proton acceptor, but neither the added carboxylato anion nor typical proton acceptors such as proton sponge assist the reaction. In [D4]MeOH, a catalytic stereospecific deuteration
Transition-Metal-Free Suzuki-Type Coupling Reactions: Scope and Limitations of the Methodology
作者:Nicholas E. Leadbeater、Maria Marco
DOI:10.1021/jo034230i
日期:2003.7.1
works well for aryl bromides, water is necessary as a solvent for the reaction, the optimum temperature for the reaction is 150 degrees C, the reaction is best performed by using microwave promotion with the exception of an electron-poor aryl bromide example where conventional heating may be used, only limited boronic acids can be used as coupling partners, sodium carbonate is the best base for the reaction
A Molecular Chameleon: Reversible pH- and Cation-Induced Control of the Optical Properties of Phthalocyanine-Based Complexes in the Visible and Near-Infrared Spectral Ranges
作者:Evgeniya A. Safonova、Alexander G. Martynov、Sergey E. Nefedov、Gayane A. Kirakosyan、Yulia G. Gorbunova、Aslan Yu. Tsivadze
DOI:10.1021/acs.inorgchem.5b02831
日期:2016.3.7
offers a unique possibility for postsynthetic modification of the optical properties of the molecules. Both aggregation of phthalocyanine and its participation in an acid–base equilibrium strongly alter their optical properties. For example, the absorption of complexes can be reversibly tuned from 686 up to 1028 nm because of the cation-induced formation of supramolecular dimers or subsequent protonation
Kinetics and mechanism of phosphine substitution for CO in [Fe2Co(CO)9(CCO)]-
作者:Stanton Ching、Duward F. Shriver
DOI:10.1021/ja00191a021
日期:1989.4
activation parameters were determined for CO substitution of (PPN)(Fesub2}Co(CO)sub 9}(CCO)) by phosphine ligands. These results along with the dependence of the reaction on the nature of the incoming ligand support an associative mechanism. Previous NMR data indicate that the phosphines selectively attack the Co metal center. Activation parameters are Delta}Hdouble dagger} = +7.2 to +10.3 kcal/mol
确定了膦配体对 (PPN)(Fesub 2}Co(CO)sub 9}(CCO)) 的 CO 取代的速率定律和活化参数。这些结果以及反应对传入配体性质的依赖性支持缔合机制。先前的 NMR 数据表明膦选择性地攻击 Co 金属中心。活化参数为 Delta}Hdouble dagger} = +7.2 to +10.3 kcal/mol 和 Delta}Sdouble dagger} = minus}34.0 to minus}45.5 cal/mol K。通过破坏金属-金属或金属-碳键来获得开放结构。溶剂极性的增加会增加配体取代率,而阳离子从 PPNsup +} 变为 Mesub 4}Nsup +} 的影响可以忽略不计。
Main-group and transition-metal complexes of 1-thia-4,7-diazacyclononane, [9]aneN2S. Crystal structures of [VOCl2([9]aneN2S)]· MeCN, [Fe([9]aneN2S)2][ClO4]2, [Zn([9]aneN2S)2][PF6]2, [Ru(cym)([9]aneN2S)][BPh4]Cl2·M eCN (cym = p-cymene), [RhCl3([9]aneN2S)]·H2O and [Tl([9]aneN2S)][ClO4]
作者:Ulrich Heinzel、Andreas Henke、Rainer Mattes
DOI:10.1039/a605999f
日期:——
A series of half-sandwich and sandwich complexes of the nine-membered
mixed donor macrocyclic 1-thia-4,7-diazacyclononane
([9]aneN
2
S) with metals in different oxidation states has
been synthesized and characterized. In each case, the ligand provides
tridentate face-capping co-ordination to the metal ion. X-Ray
crystallographic structure determinations have been performed for most
complexes; [Fe([9]aneN
2
S)
2
]
2+
and
[Zn([9]aneN
2
S)
2
]
2+
display
trans-octahedral N
4
S
2
co-ordination. The
metal–nitrogen and metal–sulfur bond distances are greater
than the respective lengths in the homoleptic complexes
[M([9]aneN
3
)
2
]
2+
and
[M([9]aneS
3
)
2
]
2+
(M = Fe
or Zn, [9]aneN
3
= 1,4,7-triazacyclononane,
[9]aneS
3
= 1,4,7-trithiacyclononane). In the
complexes of metal ions with larger radii, e.g.
Rh
III
and Tl
I
, the metal–sulfur distances
are equal to or smaller than those in the complexes of
[9]aneS
3
. The difference between the metal–nitrogen and
the metal–sulfur bond lengths varies from 0.21 Å to 0.40
Å in the complexes studied. Both λλλ and
λδλ conformations of the three chelate rings formed
were observed.