Characteristic Features of the Synthesis of 2,1,3-Benzothiadiazole-Substituted 1,3-Iminophosphine and Platinum Complex of this Compound

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Abstract

In an attempt to synthesize a new iminomethylphosphine, tBuC(Ph2P)=N-Btd (Btd = 2,1,3-benzothiadiazole) by a three-step procedure including (1) NH2-Btd + tBuC(=O)Cl → tBuC(=O)NH-Btd; (2) tBuC(=O)NH-Btd + SOCl2 → tBuC(Cl)=N-Btd; (3) tBuC(Cl)=N-Btd + Ph2PSiMe3 → tBuC(Ph2P)=N-Btd, it was found that the second step is accompanied by the chlorination of the carbocycle in the benzothiadiazole moiety. The reaction of the imidoyl chloride tBuC(Cl)=N-(7-Cl-Btd) formed in this reaction with Ph2PSiMe3 gave 1,3-iminomethylphosphine tBuC(Ph2P)=N-(7-Cl-Btd) (PC=N). The byproducts formed in this step include 1,3-aminomethylphosphine oxide tBuC{Ph2P(O)}NH-(7-Cl-Btd) (POCN) and (Ph2POx)2,, resulting from partial oxidation and hydrolysis. The reactions of PC=N and POCN with [Pt(COD)Cl2] (COD = 1.3-cyclooctadiene) were studied. In the case of PC=N, the reaction affords the [Pt(PC=N)2Cl2] complex. In the latter case, cleavage of the P–C bond in POCN takes place, and [PtCl2(Ph2POH)2](POCN) and [Pt(CH3CN){tBuC-NH-(7-Cl-Btd)}Cl]. are isolated from the reaction mixture. The structures of the new compounds were established by single-crystal X-ray diffraction (tBuC(Cl)N-(7-Cl-Btd)), 2335152 (POCN · Et2O), 2335149 (Ph2POx)2, 2335153 ([Pt(PC=N)2Cl2]), 2335154 ([PtCl2(Ph2POH)2](POCN)), 2335151 ([Pt(CH3CN)(tBuC-NH-(7-Cl-Вbtd))Cl]).

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About the authors

R. M. Khisamov

Nikolaev Institute of Inorganic Chemistry of the Siberian Branch of the Russian Academy of Sciences

Email: sukhikh@niic.nsc.ru
Russian Federation, Novosibirsk

S. N. Konchenko

Nikolaev Institute of Inorganic Chemistry of the Siberian Branch of the Russian Academy of Sciences

Email: sukhikh@niic.nsc.ru
Russian Federation, Novosibirsk

T. S. Sukhikh

Nikolaev Institute of Inorganic Chemistry of the Siberian Branch of the Russian Academy of Sciences

Author for correspondence.
Email: sukhikh@niic.nsc.ru
Russian Federation, Novosibirsk

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Supplementary files

Supplementary Files
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1. JATS XML
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2. Scheme 1. General approaches to the synthesis of 1,3-iminomethylphosphines

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3. Fig. 1. Experimental (exp.) and simulated (sim.) powder diffractograms for [PtCl2(PC=N)2] (MoKα radiation)

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4. Scheme 2. Synthesis of 1,3-iminomethylphosphine PC=N

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5. Scheme 3. Side reaction of the formation of 1,3-aminomethylphosphinoxide POCN in the presence of air

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6. Scheme 4. Reactions of iminomethylphosphine PC=N and aminomethylphosphines PCN-Pbt [26] and POCN with [Pt(COD)Cl2]

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7. Fig. 2. Structure of the disordered molecule (Ph2POx)2, H atoms are not shown. The major position is shown in colour, the minor position in black. Populations of P and O atoms are indicated

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8. Fig. 3. Structure of a single molecule of 1,3-aminomethylphosphine in POCN - 0.5Et2O (a) and a pair of molecules with contact between (C)H and O atoms (b; other H atoms not shown)

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9. Fig. 4. Structure of [PtCl2(Ph2POH)2](POCN) (a); H atoms except those involved in hydrogen bonding are not shown, and [Pt(PC=N)2Cl2] (b), H atoms are not shown

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10. Fig. 5. Structure of [Pt(CH3CN){tBuC-NH-(7-Cl-Btd)}Cl] (a) and tBuC(Cl)=N-(7-Cl-Btd) (b)

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