Solving the P–O/P–OH riddle: direct synthesis and neutron diffraction characterization of dianionic dithiophosphonates

Michael N. Pillay; Min Chi Li; Yu Rong Ni; Wei Jung Yen; Tzu Hao Chiu; Xiaoping Wang; Jean Yves Saillard; C. W. Liu

doi:10.1039/d5dt02816g

Solving the P–O/P–OH riddle: direct synthesis and neutron diffraction characterization of dianionic dithiophosphonates

Michael N. Pillay
, Min Chi Li
, Yu Rong Ni
, Wei Jung Yen
, Tzu Hao Chiu
, Xiaoping Wang
, Jean Yves Saillard
, C. W. Liu

Single Crystal Diffraction

Research output: Contribution to journal › Article › peer-review

Abstract

We report the first definitive neutron diffraction study aimed at resolving the P–OH/P 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 O structural ambiguity in metal dithiophosphonates. The small NH₄ counterion forces a rare syn-configuration via an extended hydrogen-bonding network. Neutron analysis definitively confirmed the fully deprotonated PO moiety, thus confirming the formation of a dianionic dithiophosphonate, a versatile synthon in homoleptic and heteroleptic coordination environments.

Original language	English
Journal	Dalton Transactions
DOIs	https://doi.org/10.1039/d5dt02816g
State	Accepted/In press - 2025

Funding

Single-crystal neutron diffraction performed on TOPAZ used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory, under contract no. DE-AC05-00OR22725 with UT-Battelle, LLC. Parts of research was supported by National Science and Technology Council of Taiwan (NSTC 114-2113-M-259-001-MY3).

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title = "Solving the P–O/P–OH riddle: direct synthesis and neutron diffraction characterization of dianionic dithiophosphonates",

abstract = "We report the first definitive neutron diffraction study aimed at resolving the P–OH/P 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 O structural ambiguity in metal dithiophosphonates. The small NH4 counterion forces a rare syn-configuration via an extended hydrogen-bonding network. Neutron analysis definitively confirmed the fully deprotonated PO moiety, thus confirming the formation of a dianionic dithiophosphonate, a versatile synthon in homoleptic and heteroleptic coordination environments.",

author = "Pillay, \{Michael N.\} and Li, \{Min Chi\} and Ni, \{Yu Rong\} and Yen, \{Wei Jung\} and Chiu, \{Tzu Hao\} and Xiaoping Wang and Saillard, \{Jean Yves\} and Liu, \{C. W.\}",

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year = "2025",

doi = "10.1039/d5dt02816g",

language = "English",

journal = "Dalton Transactions",

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T1 - Solving the P–O/P–OH riddle

T2 - direct synthesis and neutron diffraction characterization of dianionic dithiophosphonates

AU - Pillay, Michael N.

AU - Li, Min Chi

AU - Ni, Yu Rong

AU - Yen, Wei Jung

AU - Chiu, Tzu Hao

AU - Wang, Xiaoping

AU - Saillard, Jean Yves

AU - Liu, C. W.

PY - 2025

Y1 - 2025

N2 - We report the first definitive neutron diffraction study aimed at resolving the P–OH/P 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 O structural ambiguity in metal dithiophosphonates. The small NH4 counterion forces a rare syn-configuration via an extended hydrogen-bonding network. Neutron analysis definitively confirmed the fully deprotonated PO moiety, thus confirming the formation of a dianionic dithiophosphonate, a versatile synthon in homoleptic and heteroleptic coordination environments.

AB - We report the first definitive neutron diffraction study aimed at resolving the P–OH/P 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 O structural ambiguity in metal dithiophosphonates. The small NH4 counterion forces a rare syn-configuration via an extended hydrogen-bonding network. Neutron analysis definitively confirmed the fully deprotonated PO moiety, thus confirming the formation of a dianionic dithiophosphonate, a versatile synthon in homoleptic and heteroleptic coordination environments.

UR - https://www.scopus.com/pages/publications/105026413908

U2 - 10.1039/d5dt02816g

DO - 10.1039/d5dt02816g

M3 - Article

AN - SCOPUS:105026413908

SN - 1477-9226

JO - Dalton Transactions

JF - Dalton Transactions

ER -

Solving the P–O/P–OH riddle: direct synthesis and neutron diffraction characterization of dianionic dithiophosphonates

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