Formation of Iron−Fluorophosphorane Complexes (η5-C5H5)(CO)LFe{P(OPh)nF4-n} (L = CO, P(OPh)3;n= 0, 1) and (η5-C5H5)(CO)2Fe{P(OC6H4NMe)F2}. Nucleophilic Attack of F-toward a Trivalent Phosphorus Atom Coordinated to a Transition Metal

1999 ◽  
Vol 18 (21) ◽  
pp. 4311-4316 ◽  
Author(s):  
Kazuyuki Kubo ◽  
Kumiko Bansho ◽  
Hiroshi Nakazawa ◽  
Katsuhiko Miyoshi
Keyword(s):  
Transition Metal ◽  
Phosphorus Atom ◽  
Nucleophilic Attack ◽  
Trivalent Phosphorus

scholarly journals Transition-Metal-Free Boryl Substitution Using Silylboranes and Alkoxy Bases

Synlett ◽  
2017 ◽  
Vol 28 (11) ◽  
pp. 1258-1267 ◽  
Author(s):  
Hajime Ito ◽  
Eiji Yamamoto ◽  
Satoshi Maeda ◽  
Tetsuya Taketsugu
Keyword(s):  
Transition Metal ◽  
Functional Group ◽  
Experimental Studies ◽  
Transition Metal Catalysts ◽  
Alkyl Halides ◽  
Aryl Halides ◽  
Nucleophilic Attack ◽  
Important Class ◽  
Mechanistic Studies ◽  
Induced Reaction

Silylboranes are used as borylation reagents for organohalides in the presence of alkoxy bases without transition-metal catalysts. PhMe2Si–B(pin) reacts with a variety of aryl, alkenyl, and alkyl halides, including sterically hindered examples, to provide the corresponding organoboronates in good yields with high borylation/silylation ratios, showing good functional group compatibility. Halogenophilic attack of a silyl nucleophile on organohalides, and subsequent nucleophilic attack on the boron electrophile are identified to be crucial, based on the results of extensive theoretical and experimental studies. This boryl­ation reaction is further applied to the first direct dimesitylboryl (BMes2) substitution of aryl halides using Ph2MeSi–BMes2 and Na(O-t-Bu), affording aryldimesitylboranes, which are regarded as an important class of compounds for organic materials.1 Introduction2 Boryl Substitution of Organohalides with PhMe2Si–B(pin)/Alkoxy Bases3 Mechanistic Investigations4 DFT Mechanistic Studies Using an Artificial Force Induced Reaction (AFIR) Method5 Dimesitylboryl Substitution of Aryl Halides with Ph2MeSi–BMes2/Na(O-t-Bu)6 Conclusion

Übergangsmetall-Komplexe mit Schwefelliganden, V. Synthese, Reaktivität und Struktur von Carbonyl-, Phosphin-und Hydrazin- Eisen(II)-Komplexen mit zwei- und vierzähnigen Schwefelliganden / Transition Metal Complexes with Sulfur Ligands, V. Synthesis, Reactivity and Structure of Carbonyl-, Phosphine-, and Hvdrazin-Iron(II). Complexes with Two-and Fourdentate Sulfur Ligands

1983 ◽  
Vol 38 (8) ◽  
pp. 961-981 ◽  
Author(s):  
Dieter Sellmanir ◽  
Günther Lanzrath ◽  
Gottfried Hüttner ◽  
Laszlo Zsolnai ◽  
Carl Krüger ◽  
...  
Keyword(s):  
Transition Metal ◽  
Transition Metal Complexes ◽  
Elemental Analysis ◽  
Structure Determination ◽  
Major Product ◽  
Nucleophilic Attack ◽  
Tridentate Ligand ◽  
Dimethyl Formamide ◽  
Nucleophilic Agent ◽  
X Ray

Reaction of FeCl3 · 4 H2O with dttd2-, the dianion of 2,3,8,9-dibenzo-1.4,7,10-tetru-thiadecane, leads to the solvated [Fe(dttd)], which coordinates CO, PMe3 and N3H4 yielding [Fe(CO)2dttd], [Fe(PMe3)2dttd], [Fe(CO)PMe3(dttd)], [Fe(N2H4)2dttd] and [Fe(N2H4)CO(dttd), respectively. With H2S and [Fe(dttd)] the Fe(III) complex (PPN)2[Fe2(S)2(dttd)2] is obtained. PPh3 cannot be coordinated to [Fe(dttd)], whereas the reaction between [Fe(PPh3)(CO)3I2] and LiSC6H4SCH3yields [Fe(PPh3)CO(CH3SCeH4S)2] besides the major product [Fe(CO)2(CH3SCeH4S)2]. A PPh3 complex can be obtained also with o-benzenedithiolate, C6H4S22-: Reacting [Fe(PPh3)(CO)3I3] with Li2S2C6H4 yields the binuclear [Fe(PPh3)(CO)2C6H4S2]2. Oxidation of [Fe(N3H4)CO(dttd)] by various agents leads to [Fo(CO)dttd]2 without evidence of formation of a N2 complex intermediate. Nucleophilic attack of [Fe(CO)2(CH3SC6H4S)2] by lithium organyls as e.g. LiPh leads to the benzoylato complex [Li(THF)3][Fe(CO)(PhCO)(CH3SC6H4S)2]; the structures of the starting complex as well as of the adduct have been elucidated by X-ray structure determination. Nucleophilic attack of the corresponding [Fe(CO)2dttd] by LiPh occurs reversibly at the Fe center; by cleavage of a Fe-S bond [Fe(Ph)(CO)2dttd′]- is formed, where dttd′ is acting as a tridentate ligand. This result shows how the reactions of formally equivalent complexes like [Fe(CO)2(CH3SC6H4S)2] and [Fe(CO)2dttd] depend strongly upon the denticity of the sulfur ligands. The dependence upon the character of the nucleophilic agent is shown by the reaction of [Fe(CO)2dttd] with Li[BEt3H]; in this case again a CO ligand is attacked reversibly yielding the formyl complex [LiBEt3][Fe(HCO)CO(dttd)], the structure of which could be elucidated so far only spectroscopically as well as by elemental analysis.[Fe(Ph)(CO)gdttd′]- forms salts like e.g. (AsPh4)[Fe(Ph)(CO)2dttd]; in solution they slowly loose CO yielding e.g. binuclear (AsPh4)2[Fe(Ph)dttd]3. Attempts to isolate the anion as [Li(TMED)3]+ salt load to the loss of CO as well as of phenyl ligands yielding the paramagnetic [Fe(TMED)dttd], which is also obtained directly from [Fe(dttd)] and TMED. The phenyl complex [Fe(Ph)dttd]22- is also formed by reaction of [Fe(dttd)] with LiPh; on reaction with dimethyl-formamide it yields [Fe(DMF)dttd]2. A series of the above described compounds has been investigated by Mößbauer spectroscopy.

Cyclic Esters of Phosphorous — Phosphoric Anhydride as a Tool for Studying the “Abnormal” Biphilic Reactivity of PIII—PV Anhydride System

1973 ◽  
Vol 28 (9-10) ◽  
pp. 620-624 ◽  
Author(s):  
J. Mikolajczyk ◽  
J. Michalski ◽  
A. Zwierzak
Keyword(s):  
Phosphorus Atom ◽  
Cyclic Ester ◽  
Trivalent Phosphorus ◽  
Cyclic Esters ◽  
Phosphoric Anhydride ◽  
Starting Point ◽  
Acetic Acids

A series of esters of phosphorous-phosphoric anhydride containing cyclic ester groups at one or both phosphorus atoms were prepared. The typical biphilic character of these compounds has been found. Unexpectedly observed lack of reactivity of anhydrides containing cyclic ester groups at trivalent phosphorus atom with respect to diethylphosphoric and acetic acids is the starting point for discussion on the mechanism of acidolysis. Unusual inertness of PIII cyclic esters of phosphorous-phosphoric anhydride towards protic acids is discussed in terms of Hudson’s concept of steric retardation on quaternisation.

Synthesis of New Chiral Crown Ethers Containing Phosphine or Secondary Phosphine Oxide Units

Synthesis ◽  
2020 ◽  
Vol 52 (19) ◽  
pp. 2870-2882
Author(s):  
Péter Huszthy ◽  
Hajnalka Szabó-Szentjóbi ◽  
István Majoros ◽  
Anna Márton ◽  
Ibolya Leveles ◽  
...  
Keyword(s):  
Transition Metal ◽  
Crown Ethers ◽  
Transition Metal Complexes ◽  
Phosphine Oxide ◽  
Catalytic Reactions ◽  
Synthesis And Characterization ◽  
Secondary Phosphine ◽  
Trivalent Phosphorus ◽  
Chiral Crown Ethers

The transition-metal complexes of phosphine and secondary phosphine oxide compounds can be used in various catalytic reactions. In this paper, the synthesis and characterization of eight new crown ethers containing trivalent phosphorus in their macroring are reported. These macrocycles are promising candidates as ligands for catalytic reactions.

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