Cobalt Complexes with 1,3-Bis(trimethylsilyl)cyclopentadienyl and Substituent-Free Pn Ligands

Scherer, Otto J.; Völmecke, Thomas; Wolmershäuser, Gotthelf

doi:10.1002/(sici)1099-0682(199906)1999:6<945::aid-ejic945>3.0.co;2-i

Cited by 21 publications

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“…Each cobalt center is coordinated by three phosphorus atoms of the P 16 ligand (Figure 4). Each cobalt atom is thereby coordinated to one phosphorus atom with a shorter dative bond (2.1651(16)-2.2218 (16) ) and by two longer Co À P bonds (2.2703(16)-2.3192 (17) ). The P7 À P16 bond (2.2334 (19) ) is in the range of a single bond, but is to a certain extent remarkable.…”

Section: Methodsmentioning

confidence: 99%

“…To date, the largest neutral P n species found is [{(Bu 3 P) 2 Ni} 4 P 14 ] (B), which was synthesized by the condensation of two P 7 units starting from Li 3 P 7 ·3 DME. [14] Using P 4 as starting material, the largest structurally characterized neutral P n ligand complexes are [{CpCr(CO) 2 } 5 (P 10 )] [15] and [(Cp R M) 4 P 10 ] (M = Rh, Cp R = Cp'' = h 5 -1,3-tBu 2 C 5 H 3 ; [16] M = Co, Cp R = Cp Si = h 5 -1,3-(SiMe 3 ) 2 C 5 H 3 ) [17] (C). The structure of C is reminicent of the condensation of two cyclo-P 5 units.…”

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“…Compared to the ionic compound [Ag(h 2 -P 4 ) 2 ] + [Al{OC-(CF 3 ) 3 } 4 ] À [24] (2.329(2) ), the P8ÀP9 distance in 3 is elongated by 0.083 , but is still 0.05 shorter than in the "sideon" coordinated PÀP edge of the P 4 molecule in [ClRh-(PPh 3 ) 2 (h 2 -P 4 )] [25] (2.462(2) ). [26] Moreover, the compounds [(Cp''Rh) 4 P 10 ] [16] (Cp'' = h 5 -1,3-tBu 2 C 5 H 3 ) and [(Cp Si Co) 4 P 10 ] [17] (Cp Si = h 5 -1,3-(SiMe 3 ) 2 C 5 H 3 ), which have an analogous coordination mode in this region, have distinctly longer PÀP distances (2.624(2) and 2.4743 (15) ).…”

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“…A few years later, a German group32c presented an extensive study of the activation of P 4 in THF using [Cp″Co(CO) 2 ] [Cp″ = 1,3‐(SiMe 3 ) 2 C 5 H 3 ] and UV irradiation. The reaction of P/Co (2:1) gave a majority (30 %) of the dark red complex [(Cp″Co)(µ 3 ‐η 4:2:2 ‐P 4 ){(Cp″Cp″Co) 2 (µ‐CO)}] ( 22 ), but the black‐purple complex [{Cp″Co} 2 (μ‐η 2:2 ‐P 2 ) 2 ] ( 23 ) was also obtained (10 %) (Scheme ).…”

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Elemental Phosphorus and Electromagnetic Radiation

2014

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White phosphorus (P 4 ) is a small molecule that is mainly used as a starting material for the large-scale synthesis of most of the suitable phosphorus derivatives. The process starts with the direct reaction of P 4 with Cl 2 , and the resulting phosphorus chloride is further treated with the adequate organic substrate. This industrial process is very primitive, and for economic and environmental reasons the first oxidation step should be avoided. The observation that the conversion of white P 4 to the red allotrope is accelerated by ultraviolet light showed that the P 4 molecule is able to be activated by elec-[a] Área www.eurjic.org MICROREVIEW (Scheme 2, path b), which is actually widely studied, [4][5][6] but the straightforward addition of a nucleophile to the P 4 framework has also been investigated. [4c,4d,7] Scheme 2. (a) Method used to functionalize white phosphorus. (b) Functionalization of P 4 mediated by its coordination to a transition metal.Very meaningful reviews have classified and discussed the most significant reactivity of P 4 and the resulting products. [4,5a-5f] Nevertheless, to the best of our knowledge, until now there has been no review that summarizes the connection found between P 4 and electromagnetic radiation. With the purpose of filling this gap, herein we present the most significant known processes that involve electromagnetic radiation and the P 4 molecule. Photochemical Properties of White Phosphorus: White Phosphorus GlowThe phosphorus glow was first observed when phosphorus was discovered. Nevertheless, until the middle of the Manuel Serrano-Ruiz completed his B.Sc. degree at the San Marcos University (Peru) and he received his Ph.D. at the University of Almería (July 2010) under the supervision of Prof. A . Romerosa. His research interest is characterized by its multidisciplinary nature, including synthetic homogeneous catalysis in water, structural and characterization studies, and by a large network of collaborations. He is Collaborator Professor at the Departament of Chemistry and Physics of the University of Almeria in the department of Inorganic Chemistry (2011), coauthor of more than twenty scientific papers in peer-reviewed journals and he has been supervisor of a Ph.D. student with "Doctor Europeans Mention" (December 2012) on the synthesis and study of catalytic and photochemical properties of new water-soluble ruthenium complexes. Almeria. His research interests cover homogeneous catalysis in water and organometallics, phosphorus, photo-and bioinorganic chemistry. He has authored 110 international refereed papers, made more than 180 presentations at national and international meetings and supervised more than 14 Ph.D. students. The theses of most of them received "Doctor Europeans Mention". Pablo Lorenzo-Luis completed his B.Sc. Degree at the La Laguna University (ULL) and he received his Ph.D. from the same University (July 1998) under the supervision of Full Professor P. Gili. Soon after, he moved to ISSECC-CNR-Florence, Italy, with Dr. S. Midollini where he wo...

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“…Fragments containing up to 24 atoms have been reported and the synthetic methods are very similar to those already encountered. Direct reactions of metal complexes with E4,117,125,129,140,143,146 Li3E7143 or LiPH2147 are the most common routes, but atom transfer processes from existing poly-pnictide compounds such as Cp*FeP5 have also been given these species 148.…”

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Transition metal complexes of the naked pnictide elements

Whitmire

2018

Coordination Chemistry Reviews

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Even though transition metal compounds containing "naked" pnictide elements (E) have been known for many decades now, the chemistry of this interesting class of compound continues to provide surprises and intellectual challenges in describing new structures and interesting bonding patterns. The number of ligand sets that now support naked pnictide ligands has expanded from the traditional organometallic ligand sets to include metal alkoxides and N-heterocyclic carbene species, and complexes are known from the early transition metals to the end of the d-block. In this review, complexes are presented based on their structural similarities starting with metal-rich compounds containing isolated E atoms in a variety of coordination environments presented in order of increasing metal connectivity. Subsequently, compounds possessing Ex fragments with x ranging from 2 to 24 are presented in increasing nuclearity. Finally, structures with low ligand ratios and metal to pnictide ratios close to one are discussed, followed by compounds that have no supporting ligands and resemble metal allow fragments. Where appropriate, electron counting rules have been employed to explain observed structures and reactivity patterns. A particularly intense area of study has been the creation of inorganic-organometallic-organic polymers and frameworks based on discrete clusters with Ex fragments (2 £ x £ 6) where the Ex fragment provides a node for structure growth in combination with transition metal coordination frameworks based on Cu and Ag and suitable organic ligands. Simple oligomers, 1-dimensional polymers, 2-dimensional polymeric networks and 3-dimensional polymeric structure have all be prepared and structurally characterized. In addition to the structural data, synthetic methods are described. The review encompasses 170 references, 118 figures and nine schemes.

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Cobalt Complexes with 1,3-Bis(trimethylsilyl)cyclopentadienyl and Substituent-Free Pn Ligands

Cited by 21 publications

References 27 publications

Access to Extended Polyphosphorus Frameworks

Access to Extended Polyphosphorus Frameworks

Elemental Phosphorus and Electromagnetic Radiation

Transition metal complexes of the naked pnictide elements

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