Metal-Mediated Degradation and Reaggregation of White Phosphorus

Ehses, Markus; Romerosa, Antonio; Peruzzini, Margherita

doi:10.1007/3-540-45731-3_5

Cited by 77 publications

(62 citation statements)

References 115 publications

(111 reference statements)

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“…Few mechanistic studies have been explicitly carried out on these P 4 degradation reactions; mechanistic proposals have been put forward in various cases, 8,9 but these are not included in the coverage of the present review. The focus herein is on synthetic, structural, and spectroscopic details.…”

Section: P Activation Leading To P ≥5 Products 18mentioning

confidence: 99%

“…8 Triphosphorus ligands derived from P 4 appear generally as cyclo-P 3 units that bind to a metal in an η 3 coordination mode. Sacconi and coworkers have provided the field with many examples of cyclo-P 3 ligands crowning various transition metal centers, including the first structurally characterized example in both the terminal disposition (in a cobalt system) and as a symmetrical µ 2 : η 3 , η 3 ligand connecting two nickel centers.…”

Section: Cyclo-p 3 Units Derived From Pmentioning

confidence: 99%

“…35 Much of this seminal late-metal work has been reviewed elsewhere. 8,[36][37][38] The earliest cyclo-P 3 complexes in an ETM context were isolated as coproducts of P 4 activation chemistry. For example, the complexes (η 3 -P 3 )Mo(CO) 2 Cp, 19, and (η 3 -P 3 )Cr(CO) 2 Cp, 20, were isolated from product mixtures that resulted when the parent dimer complexes [Cp(CO) 2 Mo] 2 and…”

Section: Cyclo-p 3 Units Derived From Pmentioning

confidence: 99%

“…8,42,43 In most instances where P 4 is observed to react with a transition metal complex, the integrity of the P 4 tetrahedron is not maintained and fragmentation and/or aggregation processes transpire. In some cases, the four atoms of the P 4 tetrahedron are each incorporated into the metal complex product affording derivatives containing tetraphosphabicyclobutane, tetraphosphabutadiene, or cyclo-P 4 coordination.…”

Section: P 4 Activation Leading To P 4 Productsmentioning

confidence: 99%

“…The reaction pathways that generate the various types of P 4 ligands have been speculated upon, but detailed mechanistic studies are essentially nonexistent. 8 The structural motif involving the fewest bond cleavage events from intact P 4 is the tetraphosphabicyclobutane geometry (butterfly geometry). Only three examples of ETM P 4 -butterfly com- in the presence of P 4 in hexane solution at room temperature gave rise to a mixture of products including Cp*(CO) 2 Nb(η 4 -P 4 ) (35), (Cp*(CO)Nb(µ 2 :η 2 -P 2 )) 2 , and (Cp*Nb) 2 (P 6 ) (vide infra).…”

Section: Rearranged P 4 Productsmentioning

confidence: 99%

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Early-Transition-Metal-Mediated Activation and Transformation of White Phosphorus

2010

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Introduction 4164 2. P 4 Activation Leading to P 1 , P 2 , and P 3 Products 4165 2.1. Terminal and Bridging P 1 Ligands from P 4 4165 2.2. Bridging P 2 Ligands from P 4 4166 2.3. Cyclo-P 3 Units Derived from P 4 4168 3. P 4 Activation Leading to P 4 Products 4169 3.1. Coordination of P 4 Tetrahedra 4169 3.2. Rearranged P 4 Products 4169 4. P 4 Activation Leading to P g5 Products 4171 5. Functionalization and Transfer Methodologies 4173 5.1. Functionalization and Subsequent Reactivity of Terminal Monophosphide and Bridging Diphosphorus Complexes Derived from P 4 4173 5.2. Reactivity and Transfer Chemistry of the Cyclo-P 3 Functional Group 4174 5.3. Functionalization and Transfer Chemistry of Polyphosphorus Ligands (P g4 ) Derived from P 4 4175 6. Concluding Remarks 4175 6.1. Conclusions 4175 6.2. Future Prospects 4176 7. Acknowledgments 4176 8. References 4176

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Section: P Activation Leading To P ≥5 Products 18mentioning

confidence: 99%

Section: Cyclo-p 3 Units Derived From Pmentioning

confidence: 99%

Section: Cyclo-p 3 Units Derived From Pmentioning

confidence: 99%

Section: P 4 Activation Leading To P 4 Productsmentioning

confidence: 99%

Section: Rearranged P 4 Productsmentioning

confidence: 99%

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Early-Transition-Metal-Mediated Activation and Transformation of White Phosphorus

2010

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Pentaphosphaferrocen als verknüpfende Einheit in ein- und zweidimensionalen Polymeren

2002

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Professor Joachim Str‰hle zum 65. Geburtstag gewidmetF¸r den Aufbau diskreter supramolekularer [1] Aggregate, Netzwerke und Koordinationspolymere [2] durch Selbstorganisation werden¸blicherweise N-Heterocyclen als N-Donorliganden verwendet, um verschiedene Metallzentren miteinander zu verkn¸pfen. Im Unterschied dazu besteht unser Ziel auf diesem Gebiet in der Nutzung von P n -Ligandkomplexen als verkn¸pfende Einheiten zwischen Metallkationen, um wohlorientierte Aggregate oder eindimensionale (1D) und zweidimensionale (2D) Koordinationspolymere zu erhalten.Die Koordinationschemie von P n -Ligandkomplexen [3] an kationischen Metallzentren (au˚er metallorganischen Kationen [4] ) ist bislang auf die Nutzung von cyclo-P 3 -Ligandkomplexen wie [(triphos)M(h 3 -P 3 )] (M Co, Rh, Ir; triphos 1,1,1-Tris(diphenylphosphanylmethyl)ethan) beschr‰nkt, die in der Regel durch ein Metallion verbr¸ckte Dimere bilden. [5] Mit CuBr bilden die entsprechenden Cobaltkomplexe einen Multidecker mit einem (CuBr) 6 -Mitteldeck, [6] w‰hrend bei den Iridiumkomplexen das Kation [{(triphos)IrP 3 } 3 Cu 5 Br 4 ] erhalten wird. [7] Im Unterschied dazu konnten wir k¸rzlich zeigen, dass [{CpMo(CO) 2 } 2 (m,h 2 -P 2 )] als Baustein zur Ver-kn¸pfung von Cu I -und Ag I -Ionen unter Bildung von 1D-Polymeren wie den Komplexen 1 und 2 verwendet werden kann. [8] In Fortf¸hrung dieser Untersuchungen haben wir versucht, den cyclo-P 5 -Ligandkomplex 3 [9] einzubeziehen, dessen Reaktionsverhalten Scherer und Mitarbeiter in den letzten Jahren intensiv untersucht haben. [3f] [Ag 2 {Cp 2 Mo 2 (CO) 4 (m,h 2 :h 1 :h 1 -P 2 )} 3 (m,h 1 :h 1 -NO 3 )] I [NO 3 ] n 1 [Cu(m-Br){Cp 2 Mo 2 (CO) 4 (m,h 2 :h 1 :h 1 -P 2 )}] I 2 [Cp*Fe(h 5 -P 5 )] 3Hier bietet sich nicht nur die Mˆglichkeit zur Bildung kationischer Tripeldeckerkomplexe [10] oder zu P 5 -‹bertragungsreaktionen an, [11] es sind auch Reaktionen bekannt, bei denen der cyclo-P 5 -Ring mehr oder weniger intakt bleibt oder unter Bildung von Ketten oder auch P 4 /P 1 -, P 3 /P 2 -oder P 2 -Fragmenten gespalten wird. [3f, 10±12] In den F‰llen, in denen der cyclo-P 5 -Ring intakt bleibt, wurde h 5 :h 1 -, h 5 :h 2 -und h 5 :h 2 :h 2 :h 1 -Koordination an metallorganische Fragmente beobachtet, [13] wobei die P-P-Bindungen signifikant ver-l‰ngert wurden. Wir berichten im Folgenden erstmals sowohļ ber die Nutzung des cyclo-P 5 -Ligandkomplexes 3 zur Syn-speziellen Reflexionsmesskopfes aufgenommen. Die rasterelektronenmikroskopischen Aufnahmen wurden im elektronenmikroskopischen Labor des Instituts f¸r Physik der Technischen Universit‰t Chemnitz an einem Philips-SEM-515-Ger‰t angefertigt. Vor der Aufnahme wurden die Proben mit Gold bedampft, um sie elektrisch leitf‰hig zu machen.

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Pentaphosphaferrocene as a Linking Unit for the Formation of One- and Two-Dimensional Polymers

Bai

Вировец

Scheer

2002

Angew. Chem. Int. Ed.

146

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Metal-Mediated Degradation and Reaggregation of White Phosphorus

Cited by 77 publications

References 115 publications

Early-Transition-Metal-Mediated Activation and Transformation of White Phosphorus

Early-Transition-Metal-Mediated Activation and Transformation of White Phosphorus

Pentaphosphaferrocen als verknüpfende Einheit in ein- und zweidimensionalen Polymeren

Pentaphosphaferrocene as a Linking Unit for the Formation of One- and Two-Dimensional Polymers

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