The complexes [Ag(AsPh
  3
)
  4
]BF
  4
 and
[Au(AsPh
  3
)
  4
]BF
  4
 were prepared from
AgBF
  4
 and 4 equivalents of AsPh
  3
, and from
equimolar quantities of [Au(AsPh
  3
)Cl] and AgBF
  4
and 3 equivalents of AsPh
  3
, respectively, in dichloromethane
solution. Single crystals of the two compounds are isomorphous
(trigonal, space group R
![[3 with combining macron]](https://www.rsc.org/images/entities/char_0033_0304.gif)
,
Z = 6) and contain cations with a tetrahedral
Ag/Au–As
  4
 core. From the Ag/Au–As distances
measured at 199 K the covalent radii of four-co-ordinate
silver(
I) and gold(
I) have been calculated using
an accepted standard covalent radius for four-co-ordinate
arsenic(
III),
r(As
  III
) = 1.20 Å;
r(Au
  I
) = 1.37 Å is found to be
6% smaller than r(Ag
  I
) = 1.46 Å.
This contraction reflects the strong influence of relativistic effects
on atomic radii. From other data, r(Cu
  I
) for
four-co-ordinate copper is estimated to be 1.29 Å.