Different reactivity of the heavier group 14 element alkyne analogues Ar′MMAr′ (M = Ge, Sn; Ar′ = C6H3-2,6(C6H3-2,6-Pri2)2) with R2NO

Abstract

The reactions of the digermanium and ditin alkyne analogues Ar'MMAr' (M = Ge or Sn) with R2NO, (R2NO = Me2C(CH2)3CMe2NO or N2O), result in complete MM bond cleavage to afford the germylene :Ge(Ar')ONR2 or the germanium(II) or tin(II) hydroxides {M(Ar')(micro-OH)}2.

[{2,6‐(Me2NCH2)2C6H3}Sn(μ‐OH)W(CO)5]2: A Transition‐Metal‐Coordinated Organotin(II) Hydroxide

“…The tin atom is five-coordinate and shows a strongly distorted trigonal-bipyramidal configuration with the N(1) and O(1A) atoms occupying the axial positions and the C(1), O(1A), and W(1) atoms occupying the equatorial positions. The N(1)-Sn(1) distance of 2.501(7) Å is slightly shorter than the N-Sn distances found in the corre- 3 A [8] B [17] C [9] Sn (1) [13] Similar to the latter compound, in which the second nitrogen atom does not coordinate to the tin ion but is involved in a hydrogen bond to the water oxygen atom [N···O 2.66(3) Å], the N(2) atom in compound 3 is involved in a hydrogen bond to the hydroxido oxygen atom O(1A) with an N(2)···O(1A) distance of 2.714(1) Å. The μ-hydroxido bridge is nonsymmetric with Sn(1)-O(1) and Sn(1A)-O(1) distances of 2.068(5) and 2.231(5) Å, respectively.…”

“…While investigating the chemistry of low-valent group 14 elements [1][2][3][4][5][6] in general, and tin(II) chemistry in particular, we became aware of only one inorganic tin(II) and one organotin(II) hydroxide, namely the salt-like trinuclear oxidotin cluster Sn 3 (OH) 4 (NO 3 ) 2 [7] and the (ArЈSnOH) 2 [ArЈ = 2,6-(2,6-iPr 2 C 6 H 3 ) 2 C 6 H 3 ] compound reported by Power et al [8] Moreover, the combined oxidation and hydrolysis of [4-tBu-2,6-{(OiPr)P(O)} 2 C 6 H 2 SnCr(CO) 5 ] 2 provided the corresponding transition-metal-complexed organotin(II) hydroxide [4-tBu-2,6-{(OiPr)P(O)} 2 C 6 H 2 Sn(OH)Cr-(CO) 5 ] 2 . [9] Details of the latter will be reported in a forthcoming paper.…”

Organotin compounds containing four‐membered distannoxane [Sn(µ‐OH)]2 units

“…59 A rare example of a distannoxane where the tin atom is in a formal oxidation state of +2 is given in entry 54 of Table 1. 60 The bulky terphenyl groups provide steric protection around tin. Interestingly the coordination geometry around tin is trigonal planar.…”

Cleavage of Ge–Ge and Sn–Sn Triple Bonds in Heavy Group 14 Element Alkyne Analogues (EAriPr4)2 (E = Ge, Sn; AriPr4 = C6H3-2,6(C6H3-2,6-iPr2)2) by Reaction with Group 6 Carbonyls

“…19 or by the reaction of m-terphenyl stabilized digermynes and distannynes with R2NO or N2O. 20 However, the insertion of transition metals into E-E bonds in (EAr iPr4 )2 is a previously unknown transformation. A central feature in the geometries of complexes 1-6 is their planar rhomboid M2E2 core.…”