18 research outputs found
Synthesis and Reactivity of a Nucleophilic Palladium(II) Carbene
Two
formal palladium carbene complexes, [PCÂ(sp<sup>2</sup>)ÂP]ÂPdÂ(PR<sub>3</sub>) (<b>3</b>: R = Me; <b>4</b>: R = Ph) were isolated
and characterized from [PCÂ(sp<sup>3</sup>)ÂH<sub>2</sub>P] ([PCÂ(sp<sup>3</sup>)ÂH<sub>2</sub>P] = bisÂ[2-(di-isopropylphosphino)Âphenyl]Âmethane, <sup>i</sup>Pr<sub>2</sub>P-C<sub>6</sub>H<sub>4</sub>-CH<sub>2</sub>-C<sub>6</sub>H<sub>4</sub>-P<sup>i</sup>Pr<sub>2</sub>). Structural studies
and DFT calculations indicate that the interaction between palladium
and carbon is best described as a single bond, associated with nucleophilic
character at that carbon atom. The characteristics of <b>3</b> were probed by reactions with electrophiles (MeI), acids (MeOH and
HCl), and <i>para</i>-toluidine
C–H Activation Reactions of a Nucleophilic Palladium Carbene
The reactivity of a nucleophilic
palladium carbene, [PCÂ(sp<sup>2</sup>)ÂP]ÂPdÂ(PMe<sub>3</sub>) (<b>1</b>; [PCÂ(sp<sup>2</sup>)ÂP] = bisÂ[2-(diisopropylphosphino)Âphenyl]Âmethylene),
toward the C–H
bonds of CH<sub>3</sub>COCH<sub>3</sub>, CH<sub>3</sub>CN, Ph–CCH,
fluorene, and 9,10-dihydroanthracene was investigated. All surveyed
substrates reacted with <b>1</b>. However, there was no detectable
reaction of <b>1</b> with Ph<sub>2</sub>CH<sub>2</sub>. It is
proposed that the p<i>K</i><sub>a</sub> values of the studied
C–H bonds govern their reactivity toward <b>1</b>: our
results show that substrates with a p<i>K</i><sub>a</sub> higher than 29, such as Ph<sub>2</sub>CH<sub>2</sub> (p<i>K</i><sub>a</sub> = 32.2), do not react even with prolonged heating
Ag(I) and Tl(I) Precursors as Transfer Agents of a Pyrrole-Based Pincer Ligand to Late Transition Metals
A PNP ligand, PN<sup>pyr</sup>P ((PN<sup>pyr</sup>P)H = 2,5-bisÂ((di-<i>iso</i>-propylphosphino)Âmethyl)Âpyrrole), which employs a pyrrole unit as
a central anionic nitrogen donor, was designed. The corresponding
group 10 metal chlorides as well as iridium and ruthenium compounds
were isolated. In order to conduct this work, [(PN<sup>pyr</sup>P)ÂTl]
and [(PN<sup>pyr</sup>P)ÂAg]<sub>2</sub> were synthesized and characterized.
The thallium and silver species were paramount in the formation of
the iridium and ruthenium complexes, which could not be isolated using
(PN<sup>pyr</sup>P)H or the corresponding lithium pyrrolide salt.
Interestingly, the solid state molecular structure of [(PN<sup>pyr</sup>P)ÂTl] indicates that the metal center engages in an η<sup>2</sup> intermolecular interaction with the backbone of a neighboring pyrrole
molecule instead of the expected bonding to the phosphine arms
An Adaptable Chelating Diphosphine Ligand for the Stabilization of Palladium and Platinum Carbenes
Group 10 metal carbenes are proposed
in catalytic transformations;
however, their isolation remains difficult without the presence of
a heteroatom donor. The adaptable cis and trans coordinating ligand
P<sup>ter</sup>P (1,2-bisÂ(2-(diisopropylphosphino)Âphenyl)Âbenzene)
is key in stabilizing two-coordinate palladium and platinum(0) precursors.
Reacting these precursors with di-<i>p</i>-tolyldiazomethane
((<i>p</i>-tol)<sub>2</sub>CN<sub>2</sub>) leads to the
formation of the unprecedented trigonal-planar diarylcarbenes [(P<sup>ter</sup>P)ÂMî—»CÂ(<i>p</i>-tol)<sub>2</sub>] (M = Pd,
Pt), upon transformation of the trans coordinating ligand into a wide-bite,
cis-coordinating ligand. Both palladium and platinum diarylcarbenes
were characterized by multinuclear NMR spectroscopy. The unusual stability
of the platinum analogue allowed its characterization via X-ray crystallography.
Furthermore, the reactivity of the palladium and platinum diarylcarbenes
with Ph<sub>2</sub>SiH<sub>2</sub> and CH<sub>3</sub>I was investigated
Aryl and Benzyl C–H Activation of N‑Substituted PNP Ligands
The synthesis of the <i>N</i>-aryl-substituted PNP pro-ligands
HÂ(PN<sup>naph</sup>P) (<i>N</i>-diÂ(2-diisopropylÂphosphine-4-methylphenyl)Ânaphthylamine)
and HÂ(PN<sup>tol</sup>P) (<i>N</i>-diÂ(2-diisopropylphosphine-4-methylphenyl)-<i>o</i>-tolylamine) is reported. The corresponding iridiumÂ(III)
complexes, [(PN<sup>naph</sup>P)ÂIrÂ(H)ÂCl], [(<i>o</i>-methyl-PN<sup>tol</sup>P)ÂIrÂ(H)ÂCl], [(<i>o</i>-aryl-PN<sup>tol</sup>P)ÂIrÂ(H)ÂCl], [(PN<sup>naph</sup>P)ÂIrÂ(H)<sub>2</sub>], [(<i>o</i>-methyl-PN<sup>tol</sup>P)ÂIrÂ(H)<sub>2</sub>], and
[(<i>o</i>-aryl-PN<sup>tol</sup>P)ÂIrÂ(H)<sub>2</sub>], were also synthesized and structurally characterized, along with
reaction intermediates, demonstrating various ligand coordination
modes
C–H Activation Reactions of a Nucleophilic Palladium Carbene
The reactivity of a nucleophilic
palladium carbene, [PCÂ(sp<sup>2</sup>)ÂP]ÂPdÂ(PMe<sub>3</sub>) (<b>1</b>; [PCÂ(sp<sup>2</sup>)ÂP] = bisÂ[2-(diisopropylphosphino)Âphenyl]Âmethylene),
toward the C–H
bonds of CH<sub>3</sub>COCH<sub>3</sub>, CH<sub>3</sub>CN, Ph–CCH,
fluorene, and 9,10-dihydroanthracene was investigated. All surveyed
substrates reacted with <b>1</b>. However, there was no detectable
reaction of <b>1</b> with Ph<sub>2</sub>CH<sub>2</sub>. It is
proposed that the p<i>K</i><sub>a</sub> values of the studied
C–H bonds govern their reactivity toward <b>1</b>: our
results show that substrates with a p<i>K</i><sub>a</sub> higher than 29, such as Ph<sub>2</sub>CH<sub>2</sub> (p<i>K</i><sub>a</sub> = 32.2), do not react even with prolonged heating
Flexible Coordination of Diphosphine Ligands Leading to cis and trans Pd(0), Pd(II), and Rh(I) Complexes
A series of diphosphine ligands <sup><i>i</i></sup>Pr<sub>2</sub>P–C<sub>6</sub>H<sub>4</sub>–X–C<sub>6</sub>H<sub>4</sub>–P<sup><i>i</i></sup>Pr<sub>2</sub> (for ligand L<sup>1</sup>, X = CH<sub>2</sub>; for ligand L<sup>2</sup>, X = CH<sub>2</sub>CH<sub>2</sub>) was investigated to determine the preference for cis/trans coordination
to palladium(0), palladiumÂ(II), and rhodiumÂ(I). Increasing the length
of the bridging alkyl backbone from one to two carbons changes the
geometry of the resulting palladiumÂ(II) complexes, with L<sup>1</sup> coordinating preferentially cis, while L<sup>2</sup> coordinates
in a trans fashion. Coordination to Pd(0) leads to L<sup>1</sup>PdÂ(dba)
and L<sup>2</sup>PdÂ(dba), in which both ligands accommodate a P–M–P
angle close to 120°. L<sup>2</sup> was found to coordinate cis
in a rhodiumÂ(I) complex ([L<sup>2</sup>RhÂ(nbd)]Â[BF<sub>4</sub>], where
nbd = norbornadiene)
Synthesis and Reactivity of a Nucleophilic Palladium(II) Carbene
Two
formal palladium carbene complexes, [PCÂ(sp<sup>2</sup>)ÂP]ÂPdÂ(PR<sub>3</sub>) (<b>3</b>: R = Me; <b>4</b>: R = Ph) were isolated
and characterized from [PCÂ(sp<sup>3</sup>)ÂH<sub>2</sub>P] ([PCÂ(sp<sup>3</sup>)ÂH<sub>2</sub>P] = bisÂ[2-(di-isopropylphosphino)Âphenyl]Âmethane, <sup>i</sup>Pr<sub>2</sub>P-C<sub>6</sub>H<sub>4</sub>-CH<sub>2</sub>-C<sub>6</sub>H<sub>4</sub>-P<sup>i</sup>Pr<sub>2</sub>). Structural studies
and DFT calculations indicate that the interaction between palladium
and carbon is best described as a single bond, associated with nucleophilic
character at that carbon atom. The characteristics of <b>3</b> were probed by reactions with electrophiles (MeI), acids (MeOH and
HCl), and <i>para</i>-toluidine
Three-Coordinate Nickel Carbene Complexes and Their One-Electron Oxidation Products
The
synthesis and characterization of two new carbene complexes,
(dtbpe)ÂNiî—»CHÂ(dmp) (<b>1</b>; dtbpe = 1,2-bisÂ(di-<i>tert</i>-butylphosphino)Âethane; dmp = 2,6-dimesitylphenyl) and
(dippn)ÂNiî—»CHÂ(dmp) (<b>2</b>; dippn = 1,8-bisÂ(di-<i>iso</i>-propylphosphino)Ânaphthalene), are described. Complexes <b>1</b> and <b>2</b> were isolated by photolysis of the corresponding
side-bound diazoalkane complexes, exemplified by (dtbpe)ÂNiÂ{η<sup>2</sup>-N<sub>2</sub>CHÂ(dmp)} (<b>3</b>). The carbene complexes
feature Ni–C distances that are short and Ni–C–C
angles at the carbene carbon that are intermediate between 120°
and 180° (155.7(3)° and 152.3(3)°, respectively). The
difference between the two carbenes became obvious when their reactivity
toward 1-electron oxidizing agents was studied: the oxidation of <b>1</b> led to an internal rearrangement and the formation of a
nickelÂ(I) alkyl [{Îş<sup>2</sup>-P,C-di-<i>tert</i>-butylphosphino-di-<i>tert</i>-butyl-PCHÂ(dmp)Âethane}ÂNi]Â[BAr<sup>F</sup><sub>4</sub>] (<b>4</b>), while the oxidation of <b>2</b> allowed the isolation of an unrearranged product, formulated
as the cationic nickelÂ(III) carbene complexÂ[(dippn)ÂNiî—»CHÂ(dmp)]Â[BAr<sup>F</sup><sub>4</sub>] (<b>6</b>). Both oxidations are chemically
reversible and the respective reductions lead to the neutral carbene
complexes, <b>1</b> and <b>2</b>
Group 10 Metal Complexes Supported by Pincer Ligands with an Olefinic Backbone
The
coordination chemistry of 2,2′-bisÂ(di-<i>iso</i>-propylÂphosphino)-<i>trans</i>-stilbene (<i>t</i>PCHî—»CHP) with group
10 metal centers in a variety
of oxidation states is reported; different coordination modes were
observed depending on the oxidation state of the metal. With metal
centers in the 0 or +1 oxidation state ((<i>t</i>PCHî—»CHP)ÂNi,
[(<i>t</i>PCHî—»CHP)ÂPd]<sub>2</sub>, (<i>t</i>PCHî—»CHP)ÂNiCl, (<i>t</i>PCHî—»CHP)ÂNiI),
η<sup>2</sup> coordination of the olefin occurs, whereas, with
metals in the +2 oxidation state, C–H activation of the backbone,
followed by rapid H–X reductive elimination, was observed,
leading to an η<sup>1</sup> coordination of the backbone in
(<i>t</i>PCî—»CHP)ÂMCl (M = Ni, Pd, Pt). Employing
the methyl-substituted analogue, 2,2′-bisÂ(di-<i>iso</i>-propylphosphino)-<i>trans</i>-diphenyl-1,2-dimethylethene
(<i>t</i>PCMeî—»CMeP), forced an η<sup>2</sup> coordination of the olefin in [(<i>t</i>PCMeî—»CMeP)ÂNiCl]<sub>2</sub>Â[NiCl<sub>4</sub>]. The synthesis of the hydride complex
(<i>t</i>PCî—»CHP)ÂNiH was attempted, but, instead,
led to the formation of (<i>t</i>PCHî—»CHP)ÂNi,
indicating that the vinyl form of the backbone can function as a hydrogen
acceptor. All metal complexes were characterized by multinuclei NMR
spectroscopy, X-ray crystallography, and elemental analysis