Synthesis of Heavier Group 14 Metal Compounds from 2,6-Lutidylbis(phosphoranosulfide)

Abstract

The synthesis and characterization of various novel group 14 metal compounds derived from 2,6lutidylbisphosphoranosulfide, [(SdPPr i 2 CH 2 ) 2 C 5 H 3 N-2,6] (1), are reported. The monoanionic bis-(thiophosphinoyl) lithium complex [Li{(SdPPr i 2 CH)(SdPPr i 2 CH 2 )C 5 H 3 N-2,6}(Et 2 O)] (2) has been prepared from the reaction of 1 with an equimolar amount of n BuLi in THF. Treatment of 1 with 1 equiv of M{N(SiMe 3 ) 2 } 2 (M = Sn, Pb) afforded the 1,3-distannacyclobutane [{2-{Sn{C(Pr i 2 Pd S)}}-6-{CH 2 (Pr i 2 PdS)}}C 5 H 3 N] 2 (3) and 1,3-diplumbacyclobutane [{2-{Pb{C(Pr i 2 PdS)}}-6-{CH 2 -(Pr i 2 PdS)}}-C 5 H 3 N] 2 (4), respectively. The metathesis reaction of 2 with GeCl 2 3 (dioxane) and SnCl 2 gave the unexpected digermylgermylene Ge[GeCl 2 {(SdPPr i 2 CH)(SdPPr i 2 CH 2 )C 5 H 3 N-2,6}] 2 (5) and ionic [2,6-lutidylbis(thiophosphinoyl)methanide]tin(II) trichlorostannate [{C 5 H 3 N-2,6-(CH 2 PPr 6), respectively. The X-ray structures of 2-6 have been determined by X-ray crystallography.

Facile Synthesis of a 20‐Membered Macrocyclic Magnesium Sulfide Complex

“…Each magnesium ion is bonded to two sulfur atoms and two nitrogen atoms from the pyrazyl ring to form two six‐membered MgNCCPS metallacycles. The average Mg–N pyrazyl bond length of 2.051 Å is comparable to those found in [Mg{(Me 3 SiN=P i Pr 2 CH) 2 C 5 H 3 N‐2,6}THF] [2.061(2) Å],20 [Mg{(Me 3 SiN=PPh 2 CH) 2 C 5 H 3 N‐2,6}THF] [2.077(3) Å],20 and [Mg{(S–P i Pr 2 CH) 2 C 5 H 3 N‐2,6}] [2.122(4) Å] 21. The average Mg–S bond length of 2.407 Å is shorter than those found in [Mg{(S–P i Pr 2 CH) 2 C 5 H 3 N‐2,6}] [2.518 Å],21 [o‐C 6 H 11 PS 3 Mg(THF) 2 ] [2.644 Å],22 and [{MgOH}{(μ‐S)[μ‐N t BuP(NH t Bu) 2 ] 6 } 6 ] 6 [2.623 Å] 23.…”

“…The average Mg–N pyrazyl bond length of 2.051 Å is comparable to those found in [Mg{(Me 3 SiN=P i Pr 2 CH) 2 C 5 H 3 N‐2,6}THF] [2.061(2) Å],20 [Mg{(Me 3 SiN=PPh 2 CH) 2 C 5 H 3 N‐2,6}THF] [2.077(3) Å],20 and [Mg{(S–P i Pr 2 CH) 2 C 5 H 3 N‐2,6}] [2.122(4) Å] 21. The average Mg–S bond length of 2.407 Å is shorter than those found in [Mg{(S–P i Pr 2 CH) 2 C 5 H 3 N‐2,6}] [2.518 Å],21 [o‐C 6 H 11 PS 3 Mg(THF) 2 ] [2.644 Å],22 and [{MgOH}{(μ‐S)[μ‐N t BuP(NH t Bu) 2 ] 6 } 6 ] 6 [2.623 Å] 23. Compound 4a features a shortening of the P–C methine bond length (average: 1.718 Å) and an elongation of the P–S bond length (average: 2.012 Å) as compared with those in the neutral ligand {CH 2 ( i Pr 2 P=S)} 2 (C 4 H 2 N 2 ‐2,3) [P–C 1.820 Å and P–S 1.947 Å].…”

Synthesis and Redox Properties of PNP Pincer Complexes Based on N‐Methyl‐4,4′‐bipyridinium

“…2a was prepared according to the literature procedure. [24] Preparation of 2b: To a flame-dried 500 mL flask were placed 2a (21.9 g, 54.2 mmol) and THF (108 mL). nBuLi (65.7 mL, 108 mmol, 1.65 m in hexane) was added dropwise at 0°C, and the resulting mixture was stirred at 0°C for 1 h. Then, MeI (6.75 mL, 108 mmol) was added dropwise at 0°C.…”

Pincer Complexes with Thione Sulfur Donors

“…A more flexible counterpart of ligand 64 bearing elongated thiophosphoryl coordinating arms, 2,6-bis(diphenylphosphinosulfide)lutidine 67, was derived from the corresponding dibromide under action of i Pr 2 PLi followed by treatment with elemental sulfur (Scheme 27) [64]. Interaction of 67 with n BuLi resulted in monolithium salt 68 featuring S,N,S-coordination mode.…”