Trapping Molecular SnBr₂(OH)₂ by Tin Alkoxide Coordination: Syntheses and Molecular Structures of [MeN(CH₂CMe₂O)₂SnBr₂]₂·SnBr₂(OH)₂ and RN(CH₂CMe₂O)₂SnL [R = Me, n‐Octyl; L = Lone Pair, Cr(CO)₅, W(CO)₅, Fe(CO)₄, Br₂]

Abstract

The synthesis of the intramolecularly coordinated stannylenes and their transition-metal complexes of the type RN(CH 2 CMe 2 O) 2 SnL [1: L = lone pair, R = Me; 2: L = lone pair, R = n-octyl; 5: L =W(CO) 5 , R = Me; 6: L = Cr(CO) 5 , R = Me; 7: L =W(CO) 5 , R = n-octyl; 8: L = Fe(CO) 4 , R = Me], and of the tin(IV) compounds RN(CH 2 CMe 2 O) 2 SnBr 2 (9: R = Me), [a] 3463 [MeN(CH 2 CMe 2 O) 2 SnBr 2 ] 2 ·SnBr 2 (OH) 2 (10) and spiro-[RN(CH 2 CMe 2 O) 2 ] 2 Sn (3: R = Me; 4: R = n-octyl) is reported. The compounds were characterized by elemental analyses, 1 H, 13 C, 119 Sn, and 119 Sn magic-angle spinning (5, 6) NMR spectroscopy, electrospray mass spectrometry, and singlecrystal X-ray diffraction analysis. exhibit superior crystallization properties. They also enabled the isolation of an unprecedented trinuclear Sn-O cluster. www.eurjic.org 3469 119 Sn MAS Spectroscopy: The 119 Sn MAS NMR spectra were recorded with a Bruker Avance III 400 spectrometer using cross polarization and high-power proton decoupling [conditions: 3.7 μS (90°) pulse, 2 ms contact time, 10 s recycle delay]. For compounds Eur.

Rational Syntheses and Serendipity: Complexes [LSnPtCl2(SMe2)]2, [{LSnPtCl(SMe2)}2SnCl2], [(LSn)3(PtCl2)(PtClSnCl){LSn(Cl)OH}], and [O(SnCl)2(SnL)2] with L=MeN(CH2CMe2O)2

“…The identity of the latterc ompound in the crude reactionm ixture was confirmed by addition of an authentic sample of 4 that had been prepared by the reaction of tin(IV) tetra-tert-butoxide, Sn(OtBu) 4 Likely,the first step is the formationo f2 by the reactiono ft he tin(II) aminoalkoxide 1 with two molar equivalents of dichloridobis(dimethylsulfide)platinum(II) under releaseo fd imethylsulfide.…”

“…Like the relatedc ompounds RN(CH 2 CH 2 O) 2 SnM (R = Me, tBu, Me 2 NCH 2 CH 2 ,M eOCH 2 CH 2 ;M = lone pair,C r(CO) 5 ,W (CO) 5 ), [1][2][3][4] complex 2 forms a cis-configured dimer by means of intermolecular O!Sn coordinationt og ive four-membered Sn 2 O 2 rings with intracyclic SnÀOd istances that range between 2.065(3) (Sn(2)ÀO(31)) and 2.147(4) (Sn(1)ÀO(31)).T he Sn(1)ÀO (17) (16) and 143.228 (13), respectively,d eviat-ing considerably from the ideal value of 1808.T he Sn(1)ÀN (14) (2.324(4) )a nd Sn(2)ÀN(34) (2.286(4) )d istances are slightly different and comparable to those in 6·3CH 2 Cl 2 .The chlorido ligands at the square-planar platinum centers are cis. The Pt(1)À Cl(2) (2.3600(17) )a nd Pt(2)ÀCl(3) (2.3647(13) )d istances are longer as compared to the Pt(1)ÀCl(1) (2.3078(14) )a nd Pt(2)ÀCl(4) (2.3057 (17) )o nes reflecting as uperior trans effect of the tin(II) aminoalkoxide 1 over dimethylsulfide, Me 2 S.…”

“…[4] Small amountso fc rystalline materialo f3·2C 4 H 8 Oc ould even be isolated from as olution of 2 in dry THF upon storage for several weeks at 4 8C. [4] Small amountso fc rystalline materialo f3·2C 4 H 8 Oc ould even be isolated from as olution of 2 in dry THF upon storage for several weeks at 4 8C.…”

“…Compound 5 can be interpreted as being composed of two molecules of 2 that coordinate the hitherto unknownc entral tinc hloride oxide moiety, ClSnOSnCl, through O!Sn interactions at Sn(1)À O(1), Sn(2)ÀO (11), and Sn (2) (2) ), [4] [MeN(CH 2 CH 2 O) 2 Sn] 2 (2.447(10), 2.413 (10) ), [1] [HOC-Me 2 CH 2 N(CH 2 CMe 2 O) 2 Sn] 2 (2.561(3), 2.552 (3) ), [27] (2) ). [28] The coordination environmenta bout the Sn(1) and Sn (2) A 119 Sn NMR spectrum of 5 in CD 2 Cl 2 solution (Supporting Information,F igure S2) shows three rather broad resonancesa t d = À250 (Dn 1/2 = 558 Hz), À263 (Dn 1/2 = 560 Hz), and À278 ppm (Dn 1/2 = 523 Hz).…”

“…[1][2][3][4] Recently,w er eported the dimeric structurei ns olution and in the solid state of the model compound bis(2,8-dioxa-5aza-3,3,5,7,7-pentamethyl-1-stanna(II)bicyclo [3.3.0]octane), (LSn) 2 (1,L = MeN(CH 2 CMe 2 O) 2 ), and its transition-metal complexes [LSn!M(CO) n ] 2 (M = W, Cr,Fe; n = 4, 5). [4] In this context, we extendedt he chemistry of 1 to reactions with platinum(II) chloride, PtCl 2 ,a nd its more soluble complex dichloridobis(di-methylsulfide)platinum(II), PtCl 2 (SMe) 2 ,i no rder to prove whetheri tb ehaves as at wo-electron s-donor ligando ri nserts into PtÀCl bonds. It is well known from literature that divalent tin compounds are able to insert into PtÀCl bonds but previous research was limited to tin(II)chloride [5][6][7][8][9][10] and stannylenes of the type SnR 2 (R = CH(SiMe 3 ) 2 ,N {CH(SiMe 3 ) 2 } 2 ,N (SiMe 3 ) 2 ), [11][12][13][14] and Me 2 Si(N-2,6-iPr2 C 6 H 3 )2 Sn .…”