A Theoretical Study of Substituent Effects on Germanium−Phosphorus Triple Bonds

Lai, Chin‐Hung; Su, Ming‐Der; Chu, San‐Yan

doi:10.1021/jp0140015

Cited by 7 publications

(2 citation statements)

References 29 publications

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“…In the same manner, the energy gain upon isomerisation increases in the sequence Ge < Sn < Pb from −30.7 to −72.0 and −121.2 kJ/mol. Both trends highlight that for the heaviest congener, the initially formed [( dtbp Cbz)EP] is least thermodynamically favourable and most likely to rearrange which is in line with previous computational work by Su and co‐workers [44−46] . Consequently, such isomerisation process was only observed for the photolysis of the Pb derivative [( dtbp Cbz)PbPCO].…”

Section: Resultssupporting

confidence: 86%

Photolysis of Phosphaketenyltetrylenes with a Carbazolyl Substituent

Li,

Hinz

2023

Chemistry An Asian Journal

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Phosphaketenes of divalent group 14 compounds can potentially serve as precursors for the synthesis of heavy multiple‐bond systems. We have employed the dtbpCbz substituent (dtbpCbz=1,8‐bis(3,5‐ditertbutylphenyl)‐3,6‐ditertbutylcarbazolyl) to prepare such phosphaketenyltetrylenes [(dtbpCbz)EPCO] (E=Ge, Sn, Pb). While the phosphaketenyltetrylenes are stable at ambient conditions, they can be readily decarbonylated photolytically. For the germylene and stannylene derivatives, dimeric diphosphene‐type products [(dtbpCbz)EP]2 (E=Ge, Sn) were obtained. In contrast, photolysis of the phosphaketenylplumbylene, via isomerisation of the [(dtbpCbz)PbP] intermediate to [(dtbpCbz)PPb], afforded an unsymmetric and incompletely decarbonylated product [(dtbpCbz)2Pb2P2CO] formally comprising a [(dtbpCbz)PPb] and a [(dtbpCbz)PbPCO] moiety.

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Section: Resultssupporting

confidence: 86%

Photolysis of Phosphaketenyltetrylenes with a Carbazolyl Substituent

Li,

Hinz

2023

Chemistry An Asian Journal

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“…While examples for transition-metal complexed silylynes and germylynes have been reported, [4][5][6] triple bonds of silicon and germanium towards other main group elements have not to date been stabilized, despite theoretical predictions. [7,8] In this respect, 1,2-chlorosilane elimination has proven to be unsuccessful, while the analogous chlorostannane elimination has not been exploited for this purpose to date. This prompted us to investigate whether chlorostannane elimination might be a better alternative for generating unsaturated PSi and PGe units.…”

Section: Introductionmentioning

confidence: 99%

Bis(stannyl)phosphanyl‐Substituted Dichlorosilanes/Germanes — Potential Precursors for a Novel Strategy Toward P–Si/Ge Multiple Bonds?

et al. 2006

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Phosphorus: Inorganic ChemistryBased in part on the article Phosphorus: Inorganic Chemistry by Josef Novosad which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Kelly

2005

Encyclopedia of Inorganic Chemistry

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The element phosphorus was first discovered in 1669, and some measure of the growth of its uses and importance since then is evident from the fact that approximately half a million tons of the element are now produced annually; in addition, phosphorus‐based materials may be generated from naturally occurring phosphates, and for this reason over 130 million tons of such material are utilized per annum. Its importance to life means that natural phosphorus cycles occur; in addition, utilization of the element and its compounds is key to many industrial processes (producing products varying from pesticides to oil additives). In the laboratory, work has shown that many ‘naked’ phosphide anions can be prepared – these can even mimic organic systems, as in the case of the cyclo [P 5 ] − ligand, which binds face on to metals in the manner of the cylcopentadienyl ligand. In addition, there are many examples of transition metal complexes of ligands containing only phosphorus; these range in size from just a single phosphorus atom to complex structures containing up to 14 atoms. Away from transition metal chemistry, phosphorus forms compounds with elements from all groups of the periodic table barring the noble gases; this article provides an overview of such compounds, with special interest in compounds that have an industrial use, that stabilize unusual bonding arrangements, or that are of current interest. In the process, it highlights the ability of the element to become involved in catenation and to form small cluster units, often with many PP bonds present. Thus, group 13 compounds of the element include the industrially important phosphides and a recently prepared new class of boron–phosphorus polymer. Silicon compounds of the element often exhibit unusual structures and some of these are illustrated and reference is made to multiple‐bonded systems, including the first example of a phosphabismuthene. Sulfides such as P 4 S 10 and halides such as PCl 3 and POCl 3 are of immense industrial importance and details of such processes and the consumption levels are provided. References to recent reviews on a range of pertinent topics are provided, including PSi chemistry, phosphides, phosphorus‐based polymers, phosphorus complexes of transition metals, phosphorus‐borane chemistry, phosphane ligands, organophosphorus chemistry, and phosphorus hydrides.

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A Theoretical Study of Substituent Effects on Germanium−Phosphorus Triple Bonds

Cited by 7 publications

References 29 publications

Photolysis of Phosphaketenyltetrylenes with a Carbazolyl Substituent

Photolysis of Phosphaketenyltetrylenes with a Carbazolyl Substituent

Bis(stannyl)phosphanyl‐Substituted Dichlorosilanes/Germanes — Potential Precursors for a Novel Strategy Toward P–Si/Ge Multiple Bonds?

Phosphorus: Inorganic ChemistryBased in part on the article Phosphorus: Inorganic Chemistry by Josef Novosad which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

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