25 research outputs found
Kloning Manusia
In the last few years, very rapid progress in the cloning technology and its development towards human cloning has become a hotly-debated issue. Cloning, which is the process of formation of a number of individuals with the same genetic structure, can be done by means of embryo-splitting method and nuclear transfer. Human cloning through the nuclear transfer method is directed towards two purposes, i.e. reproduction and therapy. The relatively new transgenic technology can be combined with the cloning technique to produce clones with new genes. However, pros and cons arise concerning the development of research on human cloning, particularly cloning for reproductive purposes. Therefore, there is need for a moratorium period before human cloning can be performed in order that solutions for all kinds of problems related to safety and ethics can be found
Syntheses, Structures, and Mössbauer Effect Spectroscopy of Triple-Decker Complexes Incorporating Nonamethylferrocene
Three
new triple-decker complexes were synthesized by the reaction
of nonamethylferrocene, Cp′FeCp* (Cp′ = C<sub>5</sub>Me<sub>4</sub>H, Cp* = C<sub>5</sub>Me<sub>5</sub>), with coordinatively
unsaturated transition-metal complexes. The reaction of ruthenium
cations [(C<sub>5</sub>R<sub>5</sub>)ÂRu]<sup>+</sup> (R = H, Me) with
Cp′FeCp* afforded the purple heterometallic triple-decker complexes
[(C<sub>5</sub>R<sub>5</sub>)ÂRuÂ(μ-Cp′)ÂFeCp*]<sup>+</sup> by electrophilic addition of ruthenium to the Cp′ ring of
nonamethylferrocene. The analogous reaction with the manganese cation
[MnÂ(CO)<sub>3</sub>]<sup>+</sup> produced the blue homometallic triple-decker
complex [Cp*FeÂ(μ-Cp′)ÂFeCp*]<sup>+</sup> by abstraction
of the Cp′ ring from Cp′FeCp* and subsequent addition
of the newly generated cation [Cp*Fe]<sup>+</sup> to 1 equiv of Cp′FeCp*.
These experiments demonstrate that the asymmetry of Cp′FeCp*
gives rise to a remarkable degree of regioselectivity such that ruthenium
electrophiles add only to the Cp′ ring and never to the Cp*
ring. In a similar way, [MnÂ(CO)<sub>3</sub>]<sup>+</sup> abstracts
only the Cp′ ring from Cp′FeCp* to produce [Cp*Fe]<sup>+</sup>, which in turn adds only to the Cp′ ring of Cp′FeCp*
to produce [Cp*FeÂ(μ-Cp′)ÂFeCp*]<sup>+</sup>. Three air-stable
triple-decker complexes incorporating nonamethylferrocene, [Cp*FeÂ(μ-Cp′)ÂFeCp*]<sup>+</sup> (<b>1</b>), [CpRuÂ(μ-Cp′)ÂFeCp*]<sup>+</sup> (<b>2</b>), and [Cp*RuÂ(μ-Cp′)ÂFeCp*]<sup>+</sup> (<b>3</b>), have been characterized by NMR spectroscopy, elemental
analysis, single-crystal X-ray diffraction analysis, and temperature-dependent <sup>57</sup>Fe Mössbauer spectroscopy
Syntheses, Structures, and Mössbauer Effect Spectroscopy of Triple-Decker Complexes Incorporating Nonamethylferrocene
Three
new triple-decker complexes were synthesized by the reaction
of nonamethylferrocene, Cp′FeCp* (Cp′ = C<sub>5</sub>Me<sub>4</sub>H, Cp* = C<sub>5</sub>Me<sub>5</sub>), with coordinatively
unsaturated transition-metal complexes. The reaction of ruthenium
cations [(C<sub>5</sub>R<sub>5</sub>)ÂRu]<sup>+</sup> (R = H, Me) with
Cp′FeCp* afforded the purple heterometallic triple-decker complexes
[(C<sub>5</sub>R<sub>5</sub>)ÂRuÂ(μ-Cp′)ÂFeCp*]<sup>+</sup> by electrophilic addition of ruthenium to the Cp′ ring of
nonamethylferrocene. The analogous reaction with the manganese cation
[MnÂ(CO)<sub>3</sub>]<sup>+</sup> produced the blue homometallic triple-decker
complex [Cp*FeÂ(μ-Cp′)ÂFeCp*]<sup>+</sup> by abstraction
of the Cp′ ring from Cp′FeCp* and subsequent addition
of the newly generated cation [Cp*Fe]<sup>+</sup> to 1 equiv of Cp′FeCp*.
These experiments demonstrate that the asymmetry of Cp′FeCp*
gives rise to a remarkable degree of regioselectivity such that ruthenium
electrophiles add only to the Cp′ ring and never to the Cp*
ring. In a similar way, [MnÂ(CO)<sub>3</sub>]<sup>+</sup> abstracts
only the Cp′ ring from Cp′FeCp* to produce [Cp*Fe]<sup>+</sup>, which in turn adds only to the Cp′ ring of Cp′FeCp*
to produce [Cp*FeÂ(μ-Cp′)ÂFeCp*]<sup>+</sup>. Three air-stable
triple-decker complexes incorporating nonamethylferrocene, [Cp*FeÂ(μ-Cp′)ÂFeCp*]<sup>+</sup> (<b>1</b>), [CpRuÂ(μ-Cp′)ÂFeCp*]<sup>+</sup> (<b>2</b>), and [Cp*RuÂ(μ-Cp′)ÂFeCp*]<sup>+</sup> (<b>3</b>), have been characterized by NMR spectroscopy, elemental
analysis, single-crystal X-ray diffraction analysis, and temperature-dependent <sup>57</sup>Fe Mössbauer spectroscopy
Influence of Ligand Modifications on Structural and Spectroscopic Properties in Terphenyl Based Heavier Group 14 Carbene Homologues
The
synthesis and characterization of a series of heavier group
14 element (Ge, Sn, and Pb) carbene homologues based on the electronically
modified, 2,6-dimesityl substituted terphenyl ligands Ar<sup>#</sup>-3,5-<sup>i</sup>Pr<sub>2</sub>, Ar<sup>#</sup>-4-SiMe<sub>3</sub>, and Ar<sup>#</sup>-4-Cl (Ar<sup>#</sup>-3,5-<sup>i</sup>Pr<sub>2</sub> = C<sub>6</sub>H<sub>2</sub>-2,6-Mes<sub>2</sub>-3,5-<sup>i</sup>Pr<sub>2</sub>; Ar<sup>#</sup>-4-Cl = C<sub>6</sub>H<sub>2</sub>-2,6-Mes<sub>2</sub>-4-Cl; Ar<sup>#</sup>-4-SiMe<sub>3</sub> = C<sub>6</sub>H<sub>2</sub>-2,6-Mes<sub>2</sub>-4-SiMe<sub>3</sub>; Mes
= C<sub>6</sub>H<sub>2</sub>-2,4,6-Me<sub>3</sub>) are presented.
The consequences of introducing electron withdrawing and -releasing
substituents on the solid state structures of the newly synthesized
germylenes, stannylenes, and plumbylenes as well as their Mössbauer,
NMR and UV–vis spectroscopic properties are presented and discussed
in the context of a second order Jahn–Teller type mixing of
frontier orbitals with appropriate symmetry. Experimental findings
were supported by DFT calculations. More electron withdrawing ligands
lead to a bonding situation with higher contribution of p-orbitals
from the central heavier group 14 element in σ-bonding toward
the ligands and thus increased s-electron character of the lone pair.
Furthermore, this results in an increase in the energy separation
between the frontier orbitals. Experimentally, these changes are manifested
in narrower bending angles at the heavy tetrel atoms and hypsochromic
in their UV–vis spectra. In contrast, derivatives of more electron
rich <i>m</i>-terphenyl ligands are characterized by a smaller
HOMO–LUMO gap and wider interligand angles
Histoire et fiction : Que se serait-il passé si… ?
The
synthesis and spectroscopic and structural characterization
of an extensive series of acyclic, monomeric tetrylene dichalcogenolates
of formula MÂ(ChAr)<sub>2</sub> (M = Si, Ge, Sn, Pb; Ch = O, S, or
Se; Ar = bulky <i>m</i>-terphenyl ligand, including two
new acyclic silylenes) are described. They were found to possess several
unusual featuresî—¸the most notable of which is their strong
tendency to display acute interligand, Ch–M–Ch, bond
angles that are often well below 90°. Furthermore, and contrary
to normal steric expectations, the interligand angles were found to
become narrower as the size of the ligand was increased. Experimental
and structural data in conjunction with high-level DFT calculations,
including corrections for dispersion effects, led to the conclusion
that dispersion forces play an important role in stabilizing their acute
interligand angles
Reactivity of a Tin(II) (Iminophosphinoyl)(thiophosphinoyl)methanediide Complex Toward Sulfur: Synthesis and <sup>119</sup>Sn Mössbauer Spectroscopic Studies of [{(μ-S)SnC(PPh<sub>2</sub>NSiMe<sub>3</sub>)(PPh<sub>2</sub>S)}<sub>3</sub>Sn(μ<sub>3</sub>-S)]
Reaction of [(PPh<sub>2</sub>î—»NSiMe<sub>3</sub>)Â(PPh<sub>2</sub>î—»S)ÂCSn:]<sub>2</sub> (<b>1</b>) with
elemental sulfur in toluene afforded [{(μ-S)Sn<sup>IV</sup>CÂ(PPh<sub>2</sub>î—»NSiMe<sub>3</sub>)Â(PPh<sub>2</sub>î—»S)}<sub>3</sub>Sn<sup>II</sup>(μ<sub>3</sub>-S)] (<b>2</b>) and [CH<sub>2</sub>(PPh<sub>2</sub>î—»NSiMe<sub>3</sub>)Â(PPh<sub>2</sub>î—»S)] (<b>3</b>). Compound <b>2</b> comprises a Sn<sup>II</sup>S moiety coordinated with the
Sn<sup>IV</sup> and S atoms of a trimeric 2-stannathiomethendiide
{(PPh<sub>2</sub>î—»NSiMe<sub>3</sub>)Â(PPh<sub>2</sub>î—»S)ÂCSnÂ(μ-S)}<sub>3</sub>. Compound <b>2</b> has been characterized by NMR spectroscopy, <sup>119</sup>Sn Mössbauer studies, X-ray crystallography, and
theoretical studies. <sup>119</sup>Sn NMR spectroscopy and Mössbauer
studies show the presence of Sn<sup>IV</sup> and Sn<sup>II</sup> atoms
in <b>2</b>. X-ray crystallography suggests that the Sn<sup>II</sup>S moiety does not have multiple bond character. Theoretical
studies illustrate that the C<sub>methanediide</sub>–Sn bonds
comprise a lone pair orbital on each C<sub>methanediide</sub> atom
and an C–Sn occupied σ orbital
Reactivity of a Tin(II) (Iminophosphinoyl)(thiophosphinoyl)methanediide Complex Toward Sulfur: Synthesis and <sup>119</sup>Sn Mössbauer Spectroscopic Studies of [{(μ-S)SnC(PPh<sub>2</sub>NSiMe<sub>3</sub>)(PPh<sub>2</sub>S)}<sub>3</sub>Sn(μ<sub>3</sub>-S)]
Reaction of [(PPh<sub>2</sub>î—»NSiMe<sub>3</sub>)Â(PPh<sub>2</sub>î—»S)ÂCSn:]<sub>2</sub> (<b>1</b>) with
elemental sulfur in toluene afforded [{(μ-S)Sn<sup>IV</sup>CÂ(PPh<sub>2</sub>î—»NSiMe<sub>3</sub>)Â(PPh<sub>2</sub>î—»S)}<sub>3</sub>Sn<sup>II</sup>(μ<sub>3</sub>-S)] (<b>2</b>) and [CH<sub>2</sub>(PPh<sub>2</sub>î—»NSiMe<sub>3</sub>)Â(PPh<sub>2</sub>î—»S)] (<b>3</b>). Compound <b>2</b> comprises a Sn<sup>II</sup>S moiety coordinated with the
Sn<sup>IV</sup> and S atoms of a trimeric 2-stannathiomethendiide
{(PPh<sub>2</sub>î—»NSiMe<sub>3</sub>)Â(PPh<sub>2</sub>î—»S)ÂCSnÂ(μ-S)}<sub>3</sub>. Compound <b>2</b> has been characterized by NMR spectroscopy, <sup>119</sup>Sn Mössbauer studies, X-ray crystallography, and
theoretical studies. <sup>119</sup>Sn NMR spectroscopy and Mössbauer
studies show the presence of Sn<sup>IV</sup> and Sn<sup>II</sup> atoms
in <b>2</b>. X-ray crystallography suggests that the Sn<sup>II</sup>S moiety does not have multiple bond character. Theoretical
studies illustrate that the C<sub>methanediide</sub>–Sn bonds
comprise a lone pair orbital on each C<sub>methanediide</sub> atom
and an C–Sn occupied σ orbital
Dispersion Forces and Counterintuitive Steric Effects in Main Group Molecules: Heavier Group 14 (Si–Pb) Dichalcogenolate Carbene Analogues with Sub-90° Interligand Bond Angles
The
synthesis and spectroscopic and structural characterization
of an extensive series of acyclic, monomeric tetrylene dichalcogenolates
of formula MÂ(ChAr)<sub>2</sub> (M = Si, Ge, Sn, Pb; Ch = O, S, or
Se; Ar = bulky <i>m</i>-terphenyl ligand, including two
new acyclic silylenes) are described. They were found to possess several
unusual featuresî—¸the most notable of which is their strong
tendency to display acute interligand, Ch–M–Ch, bond
angles that are often well below 90°. Furthermore, and contrary
to normal steric expectations, the interligand angles were found to
become narrower as the size of the ligand was increased. Experimental
and structural data in conjunction with high-level DFT calculations,
including corrections for dispersion effects, led to the conclusion
that dispersion forces play an important role in stabilizing their acute
interligand angles
Dispersion Forces and Counterintuitive Steric Effects in Main Group Molecules: Heavier Group 14 (Si–Pb) Dichalcogenolate Carbene Analogues with Sub-90° Interligand Bond Angles
The
synthesis and spectroscopic and structural characterization
of an extensive series of acyclic, monomeric tetrylene dichalcogenolates
of formula MÂ(ChAr)<sub>2</sub> (M = Si, Ge, Sn, Pb; Ch = O, S, or
Se; Ar = bulky <i>m</i>-terphenyl ligand, including two
new acyclic silylenes) are described. They were found to possess several
unusual featuresî—¸the most notable of which is their strong
tendency to display acute interligand, Ch–M–Ch, bond
angles that are often well below 90°. Furthermore, and contrary
to normal steric expectations, the interligand angles were found to
become narrower as the size of the ligand was increased. Experimental
and structural data in conjunction with high-level DFT calculations,
including corrections for dispersion effects, led to the conclusion
that dispersion forces play an important role in stabilizing their acute
interligand angles
Dispersion Forces and Counterintuitive Steric Effects in Main Group Molecules: Heavier Group 14 (Si–Pb) Dichalcogenolate Carbene Analogues with Sub-90° Interligand Bond Angles
The
synthesis and spectroscopic and structural characterization
of an extensive series of acyclic, monomeric tetrylene dichalcogenolates
of formula MÂ(ChAr)<sub>2</sub> (M = Si, Ge, Sn, Pb; Ch = O, S, or
Se; Ar = bulky <i>m</i>-terphenyl ligand, including two
new acyclic silylenes) are described. They were found to possess several
unusual featuresî—¸the most notable of which is their strong
tendency to display acute interligand, Ch–M–Ch, bond
angles that are often well below 90°. Furthermore, and contrary
to normal steric expectations, the interligand angles were found to
become narrower as the size of the ligand was increased. Experimental
and structural data in conjunction with high-level DFT calculations,
including corrections for dispersion effects, led to the conclusion
that dispersion forces play an important role in stabilizing their acute
interligand angles