scholarly journals Computational Characterization of Bidentate P-Donor Ligands: Direct Comparison to Tolman’s Electronic Parameters

Molecules ◽  
2018 ◽  
Vol 23 (12) ◽  
pp. 3176 ◽  
Author(s):  
Tímea Kégl ◽  
Noémi Pálinkás ◽  
László Kollár ◽  
Tamás Kégl
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Metal Carbonyl ◽  
Donor Ligands ◽  
Carbonyl Complexes ◽  
Electronic Effects ◽  
Functional Theory ◽  
Metal Carbonyl Complexes ◽  
Electronic Parameters

The applicability of two types of transition-metal carbonyl complexes as appropriate candidates for computationally derived Tolman’s ligand electronic parameters were examined with density functional theory (DFT) calculations employing the B97D3 functional. Both Pd(0)L2(CO) and HRh(I)L2(CO) complexes correlated well with the experimental Tolman Electronic Parameter scale. For direct comparison of the electronic effects of diphosphines with those of monophosphines, the palladium-containing system is recommended. The t r a n s influence of various phosphines did not show a major difference, but the decrease of the H-Rh-P angle from linear can cause a significant change.

Metal carbonyl complexes of potentially ambidentate 2,1,3-benzothiadiazole and 2,1,3-benzoselenadiazole acceptors

2017 ◽  
Vol 72 (11) ◽  
pp. 839-846
Author(s):  
Sebastian Plebst ◽  
Martina Bubrin ◽  
David Schweinfurth ◽  
Stanislav Záliš ◽  
Wolfgang Kaim
Keyword(s):  
Crystal Structure ◽  
Density Functional Theory ◽  
Electron Transfer ◽  
Density Functional ◽  
Metal Carbonyl ◽  
Density Functional Theory Calculations ◽  
Carbonyl Complexes ◽  
Functional Theory ◽  
Metal Carbonyl Complexes ◽  
Reduced Forms

AbstractThe compounds [W(CO)5(btd)], [W(CO)5(bsd] and [Re(CO)3(bpy)(bsd)](BF4), btd=2,1,3-benzothiadiazole and bsd=2,1,3-benzoselenadiazole were isolated and characterized experimentally (crystal structure, spectroscopy, spectroelectrochemistry) and by density functional theory calculations. The results confirm single N-coordination in all cases, binding to Se was calculated to be less favorable. Studies of one-electron reduced forms indicate that the N-coordination is maintained during electron transfer.

Intra- and intermolecular interactions in a series of chlorido-tricarbonyl-diazabutadienerhenium(I) complexes: structural and theoretical studies

2020 ◽  
Vol 76 (3) ◽  
pp. 417-426 ◽  
Author(s):  
Reza Kia ◽  
Azadeh Kalaghchi
Keyword(s):  
Intermolecular Interactions ◽  
Density Functional ◽  
Metal Carbonyl ◽  
Lone Pair ◽  
Carbonyl Complexes ◽  
X Ray Diffraction ◽  
Functional Theory ◽  
X Ray ◽  
Covalent Interaction ◽  
Metal Carbonyl Complexes

A series of new chlorido-tricarbonylrhenium(I) complexes bearing alkyl-substituted diazabutadiene (DAB) ligands, namely N,N′-bis(2,4-dimethylbenzene)-1,4-diazabutadiene (L1), N,N′-bis(2,4-dimethylbenzene)-2,3-dimethyl-1,4-diazabutadiene (L2), N,N′-bis(2,4,6-trimethylbenzene)-2,3-dimethyl-1,4-diazabutadiene (L3) and N,N′-bis(2,6-diisopropylbenzene)-1,4-diazabutadiene (L4), were synthesized and investigated. The crystal structures have been fully characterized by X-ray diffraction and spectroscopic methods. Density functional theory, natural bond orbital and non-covalent interaction index methods have been used to study the optimized geometry in the gas phase and intra- and intermolecular interactions in the complexes, respectively. The most important studied interactions in these metal carbonyl complexes are n→π*, n→σ* and π→π*. Among complexes 1–4, only 2 shows interesting intermolecular n→π* interactions due to lp(C[triple-bond]O)...π* and lp(Cl)...π* (lp = lone pair) contacts.

scholarly journals Photoactivatable metal complexes: from theory to applications in biotechnology and medicine

2013 ◽  
Vol 371 (1995) ◽  
pp. 20120519 ◽  
Author(s):  
Nichola A. Smith ◽  
Peter J. Sadler
Keyword(s):  
Metal Complexes ◽  
Density Functional ◽  
Metal Carbonyl ◽  
Short Review ◽  
Photochemical Reactions ◽  
Carbonyl Complexes ◽  
Functional Theory ◽  
Metal Carbonyl Complexes ◽  
Recent Developments ◽  
Novel Strategy

This short review highlights some of the exciting new experimental and theoretical developments in the field of photoactivatable metal complexes and their applications in biotechnology and medicine. The examples chosen are based on some of the presentations at the Royal Society Discussion Meeting in June 2012, many of which are featured in more detail in other articles in this issue. This is a young field. Even the photochemistry of well-known systems such as metal–carbonyl complexes is still being elucidated. Striking are the recent developments in theory and computation (e.g. time-dependent density functional theory) and in ultrafast-pulsed radiation techniques which allow photochemical reactions to be followed and their mechanisms to be revealed on picosecond/nanosecond time scales. Not only do some metal complexes (e.g. those of Ru and Ir) possess favourable emission properties which allow functional imaging of cells and tissues (e.g. DNA interactions), but metal complexes can also provide spatially controlled photorelease of bioactive small molecules (e.g. CO and NO)—a novel strategy for site-directed therapy. This extends to cancer therapy, where metal-based precursors offer the prospect of generating excited-state drugs with new mechanisms of action that complement and augment those of current organic photosensitizers.

The siliconyl, boronyl, and iminoboryl ligands as analogues of the well-known carbonyl ligand: predicted reactivity towards dipolar cyclooligomerization in iron/cobalt carbonyl complexes

RSC Advances ◽  
2015 ◽  
Vol 5 (45) ◽  
pp. 35558-35563 ◽  
Author(s):  
Zhong Zhang ◽  
Liang Pu ◽  
Qianshu Li ◽  
R. Bruce King
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Carbonyl Complexes ◽  
Carbonyl Ligand ◽  
Cobalt Carbonyl ◽  
Functional Theory ◽  
Iron Cobalt ◽  
Single Bonds

The Fe(CO)4(SiO), Co(CO)4(BO), and Co(CO)4(BNSiMe3), complexes akin to the well-known Fe(CO)5 are predicted by density functional theory to undergo exothermic oligomerization to give the oligomers containing SinOn/BnOn/B2N2 rings with single bonds.

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