SN₂P₂: A Neutral Five‐Membered Sulfur–Pnictogen(III) Ring

Abstract

The novel aromatic ring compound 2,4-diphospha-3,5-diaza-thiole (cyclo-SNPNP) was synthesized via flash pyrolysis of SP(N3)3 and characterized by IR spectroscopy and (15)N isotope labeling. Quantum chemical computations indicate its formation by head-to-tail dimerization of SNP and subsequent elimination of a sulfur atom from the highly unstable boatlike six-membered-ring compound cyclo-SNPSNP.

Negative ion photoelectron spectroscopy of P2N3−: electron affinity and electronic structures of P2N3˙

“…During the past three decades, researchers have sought other, all-inorganic, aromatic species. For example, N 2 S 3 2+ , 20 N 3 S 2 + , 21 and SN 2 P 2 , 22 which are isolobal to cyclo -P 5 – , have been identified; but N 2 S 3 2+ is not stable in solutions (N 2 S 3 2+ ), SN 2 P 2 is only stable when isolated in an Ar matrix, and only N 3 S 2 + has proven to be stable enough for isolation. Cyclo -N 5 – , the first-row congener of cyclo -P 5 – , has only been observed in the gas phase, where it can be formed via collision induced dissociation (CID) of a compound containing the N 5 unit 23 , 24 or its presence inferred via labeling studies of azide ion produced in the decomposition.…”

Accessing an Aromatic Diphosphatriazolate Anion by Formal Inorganic “Click” Chemistry

“…[15] Just recently,Zeng, Beckers,and co-workers prepared the neutral SN 2 P 2 heterocycle (7,Scheme 2) by flash pyrolysis of SP(N 3 ) 3 at 1000 Ka nd trapped the product in an argon matrix at 16 K. This product was characterized by IR spectroscopy with structural assignments facilitated by computational investigations,w hich also suggest that 7 is formed by the head-to-tail dimerization of gaseous SNP to cyclic [SNP] 2 ,followed by loss of sulfur. [16] Thei solobal analogue of [P 2 N 3 ] À , cyclo-[P 5 ] À ,h as been explored as aligand in transition-metal chemistry as it offers additional coordination sites in relation to the ubiquitous [C 5 H 5 ] À ion. Fore xample,S cheer and co-workers demonstrated that the hybrid sandwich complex [(h 5 -Cp*)Fe(h 5 -P 5 )] (Cp* = C 5 Me 5 )c ould further coordinate with copper(I) halides.T he resulting species adopt large (nanoscale) fullerene-like topologies and represent nice examples of selfassembly.…”

“…[14] This trithiadiazolium dication is not stable in solution and its formation in the solid state is driven by the high lattice energy of the 1:2 salts. [16] Thei solobal analogue of [P 2 N 3 ] À , cyclo-[P 5 ] À ,h as been explored as aligand in transition-metal chemistry as it offers additional coordination sites in relation to the ubiquitous [C 5 H 5 ] À ion. [15] Just recently,Zeng, Beckers,and co-workers prepared the neutral SN 2 P 2 heterocycle (7,Scheme 2) by flash pyrolysis of SP(N 3 ) 3 at 1000 Ka nd trapped the product in an argon matrix at 16 K. This product was characterized by IR spectroscopy with structural assignments facilitated by computational investigations,w hich also suggest that 7 is formed by the head-to-tail dimerization of gaseous SNP to cyclic [SNP] 2 ,followed by loss of sulfur.…”

Ein aromatisches Diphosphatriazolat‐Anion durch formale anorganische “Klick”‐Chemie

“…Erst kürzlich präparierten Zeng und Beckers den neutralen SN 2 P 2 ‐Heterocyclus ( 7 , Schema ) durch Flash‐Pyrolyse von SP(N 3 ) 3 bei 1000 K und isolierten das Produkt in einer Argonmatrix bei 16 K. Dieses Ringsystem wurde durch IR‐Spektroskopie charakterisiert und die strukturelle Zuordnung durch computergestützte Studien ermöglicht. Die Untersuchungen ergaben ebenfalls, dass 7 durch Kopf‐zu‐Schwanz‐Dimerisierung von gasförmigen SNP zu cyclischem [SNP] 2 und den anschließenden Verlust von Schwefel gebildet wird 16…”