Zirconium - Phosphorus Chemistry: Strategies in Syntheses, Reactivity, Catalysis, and Utility

Stephan, Douglas W.

doi:10.1002/(sici)1521-3773(20000117)39:2<314::aid-anie314>3.0.co;2-d

Cited by 135 publications

(7 citation statements)

References 64 publications

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“…Transition metal phosphanido complexes [M–PR 2 ] are valuable species proposed to be actively involved in modern catalytic transformations . Among them, metal-mediated dehydrocoupling (DHC) of phosphane-boranes or primary and secondary phosphanes is providing an easy synthetic access to new inorganic materials, such as high molecular weight polyphosphaneboranes or phosphaneborane rings and chains .…”

Section: Introductionmentioning

confidence: 90%

Nucleophilicity and P–C Bond Formation Reactions of a Terminal Phosphanido Iridium Complex

et al. 2015

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The diiridium complex [{Ir(ABPN2)(CO)}2(μ-CO)] (1; [ABPN2](-) = [(allyl)B(Pz)2(CH2PPh2)](-)) reacts with diphenylphosphane affording [Ir(ABPN2)(CO)(H) (PPh2)] (2), the product of the oxidative addition of the P-H bond to the metal. DFT studies revealed a large contribution of the terminal phosphanido lone pair to the HOMO of 2, indicating nucleophilic character of this ligand, which is evidenced by reactions of 2 with typical electrophiles such as H(+), Me(+), and O2. Products from the reaction of 2 with methyl chloroacetate were found to be either [Ir(ABPN2)(CO)(H)(PPh2CH2CO2Me)][PF6] ([6]PF6) or [Ir(ABPN2)(CO)(Cl)(H)] (7) and the free phosphane (PPh2CH2CO2Me), both involving P-C bond formation, depending on the reaction conditions. New complexes having iridacyclophosphapentenone and iridacyclophosphapentanone moieties result from reactions of 2 with dimethyl acetylenedicarboxylate and dimethyl maleate, respectively, as a consequence of a further incorporation of the carbonyl ligand. In this line, the terminal alkyne methyl propiolate gave a mixture of a similar iridacyclophosphapentanone complex and [Ir(ABPN2){CH═C(CO2Me)-CO}{PPh2-CH═CH(CO2Me)}] (10), which bears the functionalized phosphane PPh2-CH═CH(CO2Me) and an iridacyclobutenone fragment. Related model reactions aimed to confirm mechanistic proposals are also studied.

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Section: Introductionmentioning

confidence: 90%

Nucleophilicity and P–C Bond Formation Reactions of a Terminal Phosphanido Iridium Complex

et al. 2015

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“…However, the predominant use of zirconium in chemistry is in the application of organometallic catalysis including olefin metathesis[39], ring-opening polymerizations[40], aminoalkene hydroamination[41], and other reactions. [42-44] For different catalytic and waste separation purposes, a number of different zirconium coordination complexes have been studied, however, in the context of the construction of 89 Zr-labeled bioconjugates for PET, only a handful of stable, aqueous, bio-compatible complexes are appropriate.…”

Section: Zirconium Chemistrymentioning

confidence: 99%

PET imaging with 89Zr: From radiochemistry to the clinic

Deri

Zeglis

Francesconi

et al. 2013

Nuclear Medicine and Biology

358

389

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The advent of antibody-based cancer therapeutics has led to the concomitant rise in the development of companion diagnostics for these therapies, particularly nuclear imaging agents. A number of radioisotopes have been employed for antibody-based PET and SPECT imaging, notably 64Cu, 124I, 111In, and 99mTc; in recent years, however, the field has increasingly focused on 89Zr, a radiometal with near ideal physical and chemical properties for immunoPET imaging. In the review at hand, we seek to provide a comprehensive portrait of the current state of 89Zr radiochemical and imaging research, including work into the production and purification of the isotope, the synthesis of new chelators, the development of new bioconjugation strategies, the creation of novel 89Zr-based agents for preclinical imaging studies, and the translation of 89Zr-labeled radiopharmaceuticals to the clinic. Particular attention will also be dedicated to emerging trends in the field, 89Zr-based imaging applications using vectors other than antibodies, the comparative advantages and limitations of 89Zr-based imaging compared to that with other isotopes, and areas that would benefit from more extensive investigation. At bottom, it is hoped that this review will provide both the experienced investigator and new scientist with a full and critical overview of this exciting and fast-developing field.

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“…When reacting with alkynes, these complexes are expected to undergo P–C coupling, although the final product will be strongly dependent on the particular nature of the metal complex under study. Electrophilic mononuclear complexes having bent terminal ligands usually undergo [1 + 2] cycloaddition to yield phosphirene derivatives, whereas their nucleophilic counterparts rather undergo [2 + 2] cycloaddition to yield products displaying metallaphosphacyclobutene rings …”

Section: Introductionmentioning

confidence: 99%

Divergent Reactivity of a Phosphinidene-Bridged Dimolybdenum Complex Toward 1-Alkynes: P–C, P–H, C–C, and C–H Couplings

et al. 2017

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The ability of complex [Mo 2 Cp 2 {μ-P(2,4,6-C 6 H 2 t Bu 3 )}(CO) 4 ] to promote P−C and subsequent coupling processes has been analyzed by examining reactions with alkynes. The title compound reacted at room temperature with different terminal alkynes HCCR under visible-UV light irradiation to give, in a selective way, the corresponding phosphapropenediyl derivatives [Mo 2 Cp 2 (μ−κ 1 C :η 3 C,C,P -CRCHPR*)(CO) 4 ] for R groups of varied electron-withdrawing nature, but low to medium size, such as Pr, CO 2 Me, and p-tol. These products follow from formal insertion of the alkyne into one of the Mo-phosphinidene bonds in the parent compound, with selective P−C coupling to the terminal carbon of the alkyne. In contrast, when R was the bulky t Bu group, the corresponding photochemical reactions yielded a mixture of the cis and trans isomers of the phosphanyl-and formylalkenyl-bridged complex [Mo 2 Cp 2 {μ−κ 2 C,O :η 2 C,C -CHC( t Bu)C(O)H}{μ-P(CH 2 CMe 2 )-C 6 H 2 t Bu 2 }(CO) 2 ], which follow from a complex reaction sequence involving an H−C(sp 3 ) bond cleavage along with different P−C, P−H, C−C, and C−H bond formation steps. Density functional theory calculations were carried out to rationalize the preceding observations and suggested that an isomer of the parent complex displaying a bent terminal phosphinidene ligand might be involved in all the above photochemical reactions.

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Zirconium - Phosphorus Chemistry: Strategies in Syntheses, Reactivity, Catalysis, and Utility

Cited by 135 publications

References 64 publications

Nucleophilicity and P–C Bond Formation Reactions of a Terminal Phosphanido Iridium Complex

Nucleophilicity and P–C Bond Formation Reactions of a Terminal Phosphanido Iridium Complex

PET imaging with 89Zr: From radiochemistry to the clinic

Divergent Reactivity of a Phosphinidene-Bridged Dimolybdenum Complex Toward 1-Alkynes: P–C, P–H, C–C, and C–H Couplings

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